Resist underlayer film forming composition for lithography containing hydrolyzable silane having halogen-containing carboxylic acid amide group

ABSTRACT

A resist underlayer film forming composition for lithography that can be used as a hard mask. The composition can improve pattern resolution due to having a trihalogenoacetamide skeleton. A resist underlayer film forming composition for lithography comprising a hydrolyzable silane, a hydrolysis product thereof, a hydrolysis condensate thereof, or a combination thereof as a silane, wherein the hydrolyzable silane comprises a silane having a halogen-containing carboxylic acid amide group.

TECHNICAL FIELD

The present invention relates to a composition for forming an underlayerfilm between a substrate and a resist (for example, a photoresist and anelectron beam resist) used for manufacturing a semiconductor device.More specifically, the present invention relates to a resist underlayerfilm forming composition for lithography for forming an underlayer filmused as an underlayer of a photoresist in a lithography process forproducing a semiconductor device. The present invention also relates toa method of forming a resist pattern using the underlayer film formingcomposition.

BACKGROUND ART

Microfabrication by lithography using photoresists has been carried outin production of semiconductor devices. The microfabrication is aprocessing method including forming the thin film of a photoresist on asemiconductor substrate such as a silicon wafer, irradiating the formedthin film with active light such as ultraviolet rays through a maskpattern in which a semiconductor device pattern is drawn, developing theirradiated thin film, and etching the substrate using the obtainedphotoresist pattern as a protecting film, thereby forming fineunevenness corresponding to the pattern. In recent years, however,semiconductor devices have been further integrated, and the active lightto be used has tended to have a shorter wavelength from a KrF excimerlaser (248 nm) to an ArF excimer laser (193 nm). This has raised seriousproblems of the effects of the reflection of active light from thesemiconductor substrate.

As an underlayer film between the semiconductor substrate and thephotoresist, a film known as a hard mask containing metal elements suchas silicon or titanium has been used. In this case, the resist and thehard mask have a large difference in their constituent components andthus the rate of removal by dry etching significantly depends on thekind of gas used for the dry etching. The hard mask can be removed bythe dry etching without significant reduction in the film thickness ofthe photoresist by appropriately selecting the kind of gas. As describedabove, in order to achieve various effects such as antireflectioneffect, a resist underlayer film has been disposed between thesemiconductor substrate and the photoresist in the production ofsemiconductor devices in recent years. Studies on the composition forthe resist underlayer film have been carried out up to now anddevelopment of new materials for the resist underlayer film is desiredfrom the viewpoint of diversity of required properties and the like.

For example, a resist underlayer film containing a polysiloxane using asilane having a sulfone structure has been developed (refer to PatentDocument 1).

A resist underlayer film containing a polysiloxane using a silane havinga sulfonamide structure has also been developed (refer to PatentDocument 2).

A resist underlayer film containing a polysiloxane using a silane havinga sulfone structure and an amine structure has also been developed(refer to Patent Document 3).

PRIOR ART DOCUMENTS Patent Documents

Patent Document 1: WO 2013-022099 Pamphlet

Patent Document 2: WO 2011-033965 Pamphlet

Patent Document 3: WO 2013-191203 Pamphlet

SUMMARY OF THE INVENTION Problem to be Solved by the Invention

An object of the present invention is to provide a resist underlayerfilm forming composition for lithography that can be used for producinga semiconductor device. Specifically, an object of the present inventionis to provide a resist underlayer film forming composition forlithography for forming a resist underlayer film that can be used as ahard mask. Another object of the present invention is to provide aresist underlayer film forming composition for lithography for forming aresist underlayer film that can be used as an anti-reflective coating.Another object of the present invention is to provide a resistunderlayer film for lithography that does not cause intermixing with aresist and has a high dry etching rate compared with the etching rate ofthe resist and a resist underlayer film forming composition for formingthe underlayer film.

Another object of the present invention is to provide a resistunderlayer film forming composition for forming a resist underlayer filmthat can form an excellent resist pattern shape when an upper layerresist is exposed and developed with an alkali developer or an organicsolvent and can transfer a rectangular resist pattern to the underlayerby dry etching carried out later.

Means for Solving the Problem

The present invention includes, as a first aspect, a resist underlayerfilm forming composition for lithography comprising: a hydrolyzablesilane, a hydrolysis product thereof, a hydrolysis condensate thereof,or a combination thereof as a silane, in which the hydrolyzable silanecomprises a hydrolyzable silane having a halogen-containing carboxylicacid amide group,

As a second aspect, the resist underlayer film forming compositionaccording to the first aspect, in which the hydrolyzable silane having ahalogen-containing carboxylic acid amide group is a hydrolyzable silaneof Formula (1):

R¹ _(a)R² _(b)Si(R³)_(4-(a+b))  Formula (1)

(in Formula (1), R¹ is an organic group of Formula (2):

(in Formula (2), R⁴ is an organic group optionally having an amidegroup, an amino group, an ether group, or a sulfonyl group and theorganic group is a C₁₋₁₀ alkylene group, an arylene group, or acombination thereof; R⁵ is a hydrogen atom or a C₁₋₁₀ alkyl group; R⁶ isan organic group substituted with a halogen atom or an organic grouphaving a halogen ion and the organic group is a C₁₋₁₀ alkyl group, aC₃₋₂₀ cyclic alkyl group, a C₁₋₁₀ alkylene group, a C₆₋₄₀ aryl group, aC₆₋₄₀ arylene group, a heterocyclic group, or a combination thereofoptionally having a sulfonyl group, a thiol group, an ether group, or acarbonyl group) and is bonded to a silicon atom through a Si—C bond; R²is an organic group having an alkyl group, an aryl group, a halogenatedalkyl group, a halogenated aryl group, an alkoxyaryl group, an alkenylgroup, or an epoxy group, an acryloyl group, a methacryloyl group, amercapto group, an amino group, or a cyano group and is bonded to asilicon atom through a Si—C bond; R³ is an alkoxy group, an acyloxygroup, or a halogen group; a is an integer of 1, b is an integer of 0 to2, and a+b is an integer of 1 to 3),

as a third aspect, the resist underlayer film forming compositionaccording to the first aspect or the second aspect, in which a halogenatom in the halogen-containing carboxylic acid amide group is a fluorineatom,

as a fourth aspect, the resist underlayer film forming compositionaccording to the first aspect or the second aspect, in which thehalogen-containing carboxylic acid amide group is a trifluoroacetamidegroup,

as a fifth aspect, the resist underlayer film forming compositionaccording to any one of the first aspect to the fourth aspect, in whichthe hydrolyzable silane is a combination of the hydrolyzable silane ofFormula (1) and other hydrolyzable silane, and the other hydrolyzablesilane is at least one hydrolyzable silane selected from the groupconsisting of a hydrolyzable silane of Formula (3):

R⁷ _(c)Si(R⁸)_(4-c)  Formula (3)

(in Formula (3), R⁷ is an organic group having an alkyl group, an arylgroup, a halogenated alkyl group, a halogenated aryl group, analkoxyaryl group, an alkenyl group, or an epoxy group, an acryloylgroup, a methacryloyl group, a mercapto group, or a cyano group and isbonded to a silicon atom through a Si—C bond; R⁸ is an alkoxy group, anacyloxy group, or a halogen group; and c is an integer of 0 to 3) and ahydrolyzable silane of Formula (4):

R⁹ _(d)Si(R¹⁰)_(3-d)

₂Y_(e)  Formula (4)

(in Formula (4), R⁹ is an alkyl group and is bonded to a silicon atomthrough a Si—C bond; R¹⁰ is an alkoxy group, an acyloxy group, or ahalogen group; Y is an alkylene group or an arylene group; d is aninteger of 0 or 1; and e is an integer of 0 or 1),

as a sixth aspect, the resist underlayer film forming compositionaccording to the first aspect, in which the resist underlayer filmforming composition comprises a hydrolysis condensate of a hydrolyzablesilane made of a combination of the hydrolyzable silane of Formula (1)according to the second aspect and the hydrolyzable silane of Formula(3) according to the fifth aspect as a polymer,

as a seventh aspect, the resist underlayer film forming compositionaccording to any one of the first aspect to the sixth aspect, furthercomprising an acid,

as an eighth aspect, the resist underlayer film forming compositionaccording to any one of the first aspect to the seventh aspect, furthercomprising water,

as a ninth aspect, a resist underlayer film formed on a semiconductorsubstrate and made of a cured product of the resist underlayer filmforming composition according to any one of the first aspect to theeighth aspect,

as a tenth aspect, a method for manufacturing a semiconductor devicecomprising: applying the resist underlayer film forming compositionaccording to any one of the first aspect to the eighth aspect onto asemiconductor substrate and baking the applied composition to form aresist underlayer film; applying a resist composition onto the resistunderlayer film to form a resist film; exposing the resist film tolight; developing the resist film after exposure to obtain a resistpattern; etching the resist underlayer film using the resist pattern;and processing the semiconductor substrate using the patterned resistfilm and resist underlayer film, and

as an eleventh aspect, a method for manufacturing a semiconductor devicecomprising: forming an organic underlayer film on a semiconductorsubstrate; applying a resist underlayer film forming compositionaccording to any one of the first aspect to the eighth aspect onto theorganic underlayer film and baking the applied composition to form aresist underlayer film; applying a resist composition onto the resistunderlayer film to form a resist film; exposing the resist film tolight; developing the resist film after exposure to obtain a resistpattern; etching the resist underlayer film using the resist pattern;etching the organic underlayer film using the patterned resistunderlayer film; and processing the semiconductor substrate using thepatterned organic underlayer film.

Effects of the Invention

The resist underlayer film formed from the resist underlayer filmforming composition for lithography of the present invention functionsas a hard mask and can be used as an anti-reflective coating. Thecomposition of the present invention does not cause intermixing with theresist.

The resist film tends to become thin in order to prevent patterncollapse when a fine pattern is formed. The dry etching for transferringthe pattern to the film existing at the underlayer is required to have ahigher etching rate than that of the upper layer film due to thinning ofthe resist. To this requirement, the resist underlayer film formingcomposition of the present invention can provide a resist underlayerfilm for lithography having a higher dry etching rate than that of aresist.

In order to control the resist shape in any development process of anygeneration of lithography, the acidity of the underlayer film isrequired to be adjusted. In particular, the skeleton generating acidwith light of each wavelength such as KrF, ArF, and EUV, and EB canenhance the contrast of the photoresist and is considered to be useful.

The resist underlayer film forming composition of the present inventionincludes a hydrolyzable silane having a halogen-containing carboxylicacid amide group, in particular a trifluoroacetamide group. Accordingly,the composition of the present invention can improve pattern resolutionparticularly in ArF exposure and EUV exposure due to having atrifluoroacetamide skeleton that can generate an acid by exposure.

MODES FOR CARRYING OUT THE INVENTION

The present invention includes a resist underlayer film formingcomposition for lithography comprising: a hydrolyzable silane, ahydrolysis product thereof, a hydrolysis condensate thereof, or acombination thereof as a silane, in which the hydrolyzable silanecomprises a hydrolyzable silane having a halogen-containing carboxylicacid amide group.

More specifically, the resist underlayer film forming composition of thepresent invention comprises a hydrolyzable silane of Formula (1) or thehydrolyzable silane of Formula (1) and other hydrolyzable silane (forexample, a hydrolyzable silane of Formula (3)), a hydrolysis productthereof, or a hydrolysis condensate thereof and a solvent. As optionalcomponents, an acid, water, an alcohol, a curing catalyst, an acidgenerator, another organic polymer, a light absorbing compound, asurfactant, and the like can be contained.

In the total silane, the hydrolyzable silane of Formula (1) can be used,for example, in a range of 50 mol % or less, or 0.05 mol % to 50 mol %,0.1 mol % to 30 mol %, or 0.1 mol % to 10 mol %.

The solid content in the resist underlayer film forming composition ofthe present invention is, for example, 0.1% by mass to 50% by mass, 0.1%by mass to 30% by mass, or 0.1% by mass to 25% by mass. Here, the solidcontent is the content of the remaining components formed by removingthe solvent components from the whole components of the resistunderlayer film forming composition.

The ratio of the hydrolyzable silane, the hydrolysis product thereof,and the hydrolysis condensate thereof contained in the solid content is20% by mass or more, and for example, 50% by mass to 100% by mass, 60%by mass to 99% by mass, or 70% by mass to 99% by mass.

The hydrolyzable silane, the hydrolysis product thereof, and thehydrolysis condensate thereof can be used as a mixture thereof. Acompound formed by condensing a hydrolysis product obtained byhydrolyzing the hydrolyzable silane can be used as the condensate. Amixture can also be used in which the hydrolysis condensate is mixedwith a partial hydrolysis product or a silane compound in whichhydrolysis is not fully completed at the time of obtaining thehydrolysis condensate. The condensate is a polymer having a polysiloxanestructure. This polysiloxane includes a hydrolysis condensate made ofthe hydrolyzable silane of Formula (1) or a combination of thehydrolyzable silane of Formula (1) and other hydrolyzable silane (forexample, a hydrolyzable silane of Formula (3)). In addition, thehydrolyzable silane of Formula (1) or a hydrolyzable silane made of acombination of the hydrolyzable silane of Formula (1) and thehydrolyzable silane of Formula (3) can be added to the hydrolysiscondensate (a polysiloxane) of the hydrolysis product made of thehydrolyzable silane of Formula (1) or the hydrolyzable silane made of acombination of the hydrolyzable silane of Formula (1) and thehydrolyzable silane of Formula (3).

In Formula (1), R¹ is an organic group of Formula (2) and is bonded tothe silicon atom through a Si—C bond. R² is an organic group having analkyl group, an aryl group, a halogenated alkyl group, a halogenatedaryl group, an alkoxyaryl group, an alkenyl group, or an epoxy group, anacryloyl group, a methacryloyl group, a mercapto group, an amino group,or a cyano group and is bonded to a silicon atom through a Si—C bond. R³is an alkoxy group, an acyloxy group, or a halogen group. a is aninteger of 1, b is an integer of 0 to 2, and a+b is an integer of 1 to3.

In Formula (2), R⁴ is an organic group optionally having an amide group,an amino group, an ether group, or a sulfonyl group and the organicgroup is a C₁₋₁₀ alkylene group, an arylene group, or a combinationthereof. R⁵ is a hydrogen atom or a C₁₋₁₀ alkyl group. R⁶ is an organicgroup substituted with a halogen atom or an organic group having ahalogen ion and the organic group is a C₁₋₁₀ alkyl group, a C₁₋₁₀alkylene group, a C₆₋₄₀ aryl group, a C₆₋₄₀ arylene group, aheterocyclic group, or a combination thereof optionally having asulfonyl group, a thiol group, an ether group, or a carbonyl group.

The alkyl group includes a linear or branched C₁₋₁₀ alkyl group andexamples of the alkyl group include methyl group, ethyl group, n-propylgroup, i-propyl group, n-butyl group, i-butyl group, s-butyl group,t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butylgroup, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group,1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group,1-ethyl-n-propyl group, n-hexyl, 1-methyl-n-pentyl group,2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentylgroup, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group,1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group,2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butylgroup, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group,1,22-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, and1-ethyl-2-methyl-n-propyl group.

The cyclic alkyl group can also be used and examples of C₃₋₂₀ cyclicalkyl groups include cyclopropyl group, cyclobutyl group,1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, cyclopentylgroup, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group,3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group,2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group,2-ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group,2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group,1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutylgroup, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group,2,2-dimethyl-cyclobutyl group, 2, 3-dimethyl-cyclobutyl group,2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group,1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group,1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group,1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group,2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group,2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group,2-ethyl-3-methyl-cyclopropyl group, adamantane group, norbornene group,and norbornane group.

Examples of the alkylene group include an alkylene group derived fromthe above alkyl group. For example, methylene group, ethylene group, andpropylene group are derived from methyl group, ethyl group, and propylgroup, respectively.

The alkenyl group includes a C₂₋₁₀ alkenyl group and examples of thealkenyl group include ethenyl group, 1-propenyl group, 2-propenyl group,1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenylgroup, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group,1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenylgroup, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenylgroup, 1-n-propylethenyl group, 1-methyl-1-butenyl group,1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-ethyl-2-propenylgroup, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group,2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenylgroup, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group,1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group,1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenylgroup, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group,3-hexenyl group, 4-hexenyl group, 5-hexenyl group, l-methyl-1-pentenylgroup, l-methyl-2-pentenyl group, 1-methyl-3-pentenyl group,1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenylgroup, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group,2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group,3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group,3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenylgroup, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group,4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group,1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group,1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group,1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group,1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group,1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group,1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group,2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group,3,3-dimethyl-1-butenyl group, l-ethyl-1-butenyl group, 1-ethyl-2-butenylgroup, l-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group,1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenylgroup, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group,1-t-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group,1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group,1-i-propyl-1-propenyl group, 1-i-propyl-2-propenyl group,1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group,2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group,2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group,2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group,3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group,3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group,3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group,1-cyclohexenyl group, 2-cyclohexenyl group, and a 3-cyclohexenyl group.

The aryl group includes a C₆₋₄₀ aryl group and examples of the arylgroup include phenyl group, o-methylphenyl group, m-methylphenyl group,p-methylphenyl group, o-chlorophenyl group, m-chlorophenyl group,p-chlorophenyl group, o-fluorophenyl group, p-mercaptophenyl group,o-methoxyphenyl group, p-methoxyphenyl group, p-aminophenyl group,p-cyanophenyl group, α-naphthyl group, β-naphthyl group, o-biphenylylgroup, m-biphenylyl group, p-biphenylyl group, 1-anthryl group,2-anthryl group, 9-anthryl group, I-phenanthryl group, 2-phenanthrylgroup, 3-phenanthryl group, 4-phenanthryl group, and 9-phenanthrylgroup.

Examples of the arylene group include an arylene group derived from theabove aryl group. For example, phenylene group and naphthylene group arederived from phenyl group and naphthyl group, respectively.

Examples of the organic group having an epoxy group includeglycidoxymethyl group, glycidoxyethyl group, glycidoxypropyl group,glycidoxybutyl group, and epoxycyclohexyl group.

Examples of the organic group having an acryloyl group includeacryloylmethyl group, acryloylethyl group, and acryloylpropyl group.

Examples of the organic group having a methacryloyl group includemethacryloylmethyl group, methacryloylethyl group, andmethacryloylpropyl group.

Examples of the organic group having a mercapto group includeethylmercapto group, butylmercapto group, hexylmercapto group, andoctylmercapto group.

Examples of the organic group having an amino group include amino group,aminomethyl group, and aminoethyl group.

Examples of the organic group having a cyano group include cyanoethylgroup and cyanopropyl group.

The alkoxy group includes an alkoxy group having a linear, branched, orcyclic alkyl moiety having a carbon atom number of 1 to 20. Examples ofthe alkoxy group having the linear and branched alkyl moiety includemethoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxygroup, i-butoxy group, s-butoxy group, t-butoxy group, n-pentyloxygroup, 1-methyl-n-butoxy group, 2-methyl-n-butoxy group,3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group,1,2-dimethyl-n-propoxy group, 2,2-dimethyl-n-propoxy group,1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group,2-methyl-n-pentyloxy group, 3-methyl-n-pentyloxy group,4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group,1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group,2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group,3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxygroup, 1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group,1-ethyl-1-methyl-n-propoxy group, and 1-ethyl-2-methyl-n-propoxy group.Examples of the alkoxy group having the cyclic alkyl moiety includecyclopropoxy group, cyclobutoxy group, 1-methyl-cyclopropoxy group,2-methyl-cycopropoxy group, cyclopentyloxy group, 1-methyl-cyclobutoxygroup, 2-methyl-cyclobutoxy group, 3-methyl-cyclobutoxy group,1,2-dimethyl-cyclopropoxy group, 2,3-dimethyl-cyclopropoxy group,1-ethyl-cyclopropoxy group, 2-ethyl-cyclopropoxy group, cyclohexyloxygroup, 1-methyl-cyclopentyloxy group, 2-methyl-cyclopentyloxy group,3-methyl-cyclopentyloxy group, 1-ethyl-cyclobutoxy group,2-ethyl-cyclobutoxy group, 3-ethyl-cyclobutoxy group,1,2-dimethyl-cyclobutoxy group, 1,3-dimethyl-cyclobutoxy group,2,2-dimethyl-cyclobutoxy group, 2,3-dimethyl-cyclobutoxy group,2,4-dimethyl-cyclobutoxy group, 3,3-dimethyl-cyclobutoxy group,1-n-propyl-cyclopropoxy group, 2-n-propyl-cyclopropoxy group,1-i-propyl-cyclopropoxy group, 2-i-propyl-cyclopropoxy group,1,2,2-trimethyl-cyclopropoxy group, 1,2,3-trimethyl-cyclopropoxy group,2,2,3-trimethyl-cyclopropoxy group, 1-ethyl-2-methyl-cyclopropoxy group,2-ethyl-1-methyl-cyclopropoxy group, 2-ethyl-2-methyl-cyclopropoxygroup, and 2-ethyl-3-methyl-cyclopropoxy group. The alkoxyaryl group isan aryl group substituted with an alkoxy group and examples of thealkoxyaryl group include methoxyphenyl group and ethoxyphenyl group.

The acyloxy group includes the C₂₋₂₀ acyloxy group and examples of theacyloxy group include methylcarbonyloxy group, ethylcarbonyloxy group,n-propylcarbonyloxy group, i-propylcarbonyloxy group, n-butylcarbonyloxygroup, i-butylcarbonyloxy group, s-butylcarbonyloxy group,t-butylcarbonyloxy group, n-pentylcarbonyloxy group,1-methyl-n-butylcarbonyloxy group, 2-methyl-n-butylcarbonyloxy group,3-methyl-n-butylcarbonyloxy group, 1,1-dimethyl-n-propylcarbonyloxygroup, 1,2-dimethyl-n-propylcarbonyloxy group,2,2-dimethyl-n-propylcarbonyloxy group, 1-ethyl-n-propylcarbonyloxygroup, n-hexylcarbonyloxy group, 1-methyl-n-pentylcarbonyloxy group,2-methyl-n-pentylcarbonyloxy group, 3-methyl-n-pentylcarbonyloxy group,4-methyl-n-pentylcarbonyloxy group, 1,1-dimethyl-n-butylcarbonyloxygroup, 1,2-dimethyl-n-butylcarbonyloxy group,1,3-dimethyl-n-butylcarbonyloxy group, 2,2-dimethyl-n-butylcarbonyloxygroup, 2,3-dimethyl-n-butylcarbonyloxy group,2,2-dimethyl-n-butylcarbonyloxy group, 2,3-dimethyl-n-butylcarbonyloxygroup, 3,3-dimethyl-n-butylcarbonyloxy group,1,1,2-trimethyl-n-butylcarbonyloxy group, 2-ethyl-n-butylcarbonyloxygroup, 1,1,2-trimethyl-n-propylcarbonyloxy group,1,2,2-trimethyl-n-propylcarbonyloxy group,1-ethyl-1-methyl-n-propylcarbonyloxy group,1-ethyl-2-methyl-n-propylcarbonyloxy group, phenylcarbonyloxy group, andtosylcarbonyloxy group.

The halogenated alkyl group and the halogenated aryl group are, forexample, the above alkyl group and aryl group substituted with a halogengroup. Examples of the halogen group include fluorine, chlorine,bromine, and iodine.

As described above, Formula (2) is a functional group having acarboxylic acid amide structure.

In Formula (2), R⁶ is an organic group substituted with a halogen atomor an organic group having a halogen ion. Examples of the halogeninclude fluorine, chlorine, bromine, and iodine.

Examples of the organic group substituted with a halogen atom include anorganic group of a C₁₋₁₀ alkyl group, a C₁₋₁₀ alkylene group, a C₆₋₄₀aryl group, a C₆₋₄₀ arylene group, and a heterocyclic group in whichsome of or all of the hydrogen atoms are substituted with halogen atoms.

As an organic group having a halogen ion, a part of a heterocyclicstructure forms a salt and the halogen ion can be contained as an anioncomponent

Examples of the alkyl group substituted with halogen atoms includeperfluoromethyl group (that is, trifluoromethyl group), perfluoroethylgroup, perfluoropropyl group, and perfluorobutyl group.

The hydrolyzable silane of Formula (1) can be exemplified as follows.

T in each of the following formulas is a C₁₋₁₀ alkyl group, for example,methyl group or ethyl group can be preferably used. In the case where Tis methyl group, the hydrolyzable group is methoxy group and in the casewhere T is ethyl group, the hydrolyzable group is ethoxy group.

As the halogen atom of the halogen-containing carboxylic acid amidegroup used in the present invention, a fluorine atom can be preferablyused. As the halogen-containing carboxylic acid amide group, atrifluoroacetamide group can be used.

In the present invention, the hydrolyzable silane includes a combinationof the hydrolyzable silane of Formula (1) and other hydrolyzable silane.As the other hydrolyzable silane, at least one hydrolyzable silaneselected from the group consisting of the hydrolyzable silane of Formula(3) and the hydrolyzable silane of Formula (4) can be used.

In Formula (3), R⁷ is an organic group having an alkyl group, an arylgroup, a halogenated alkyl group, a halogenated aryl group, analkoxyaryl group, an alkenyl group, or an epoxy group, an acryloylgroup, a methacryloyl group, a mercapto group, or a cyano group and isbonded to a silicon atom through a Si—C bond. R⁸ is an alkoxy group, anacyloxy group, or a halogen group. c is an integer of 0 to 3.

In Formula (4), R⁹ is an alkyl group and is bonded to a silicon atomthrough a Si—C bond. R¹⁰ is an alkoxy group, an acyloxy group, or ahalogen group. Y is an alkylene group or an arylene group. d is aninteger of 0 or 1 and e is an integer of 0 or 1.

The above examples can be used as the organic group having the alkylgroup, the aryl group, the halogenated alkyl group, the halogenated arylgroup, the alkoxyaryl group, the alkenyl group, or the epoxy group, theacryloyl group, the methacryloyl group, the mercapto group, or the cyanogroup, and the alkoxy group, the acyloxy group, and the halogen group.

Examples of the silicon-containing compound of Formula (3) includetetramethoxysilane, tetrachlorosilane, tetraacetoxysilane,tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane,tetra-n-butoxysilane, methyltrimethoxysilane, methyltrichlorosilane,methyltriacetoxysilane, methyltripropoxy silane,methyltributyloxysilane, methyltriamyloxysilane, methyltriphenoxysilane,methyltribenzyloxysilane, methyltriphenethyloxysilane,glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane,α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane,β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane,α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane,β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane,γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane,γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane,α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane,γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane,8-glycidoxybutyltrimethoxysilane, 8-glycidoxybutyltriethoxysilane,(3,4-epoxycyclohexyl)methyltrimetboxysilane,(3,4-epoxycyclohexyl)methyltriethoxysilane,β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,β-(3,4-epoxycyclohexyl)ethyltriethoxysilane,β-(3,4-epoxycyclohexyl)ethyltripropoxysilane,β-(3,4-epoxycyclohexyl)ethyltributoxysilane,β-(3,4-epoxycyclohexyl)ethyltriphenoxysilane,γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane,γ-(3,4-epoxycyclohexyl)propyltriethoxysilane,δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane,δ-(3,4-epoxycyclohexyl)butyltriethoxysilane,glycidoxymethylmethyldimethoxysilane,glycidoxymethylmethyldiethoxysilane,α-glycidoxyehynethyldimethoxysilane,α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-gycidoxyethylethyl dimethoxysilane,α-glycidoxypropylmethyldimethoxysilane,α-glycidoxypropylmethyldiethoxysilane,β-glycidoxypropylmethyldimethoxysilane,β-glycidoxypropylethyldimethoxysilane,γ-glycidoxypropylmethyldimethoxysilane,γ-glycidoxypropylmethyldiethoxysilane,γ-glycidoxypropylmethyldipropoxysilane,γ-glycidoxypropylmethyldibutoxysilane,γ-glycidoxypropylmethyldiphenoxysilane,γ-glycidoxypropylethyldimethoxysilane,γ-glycidoxypropylethyldiethoxysilanc,γ-glycidoxypropylvinyldimethoxysilane,γ-glycidoxypropylvinyldiethoxysilane, ethyltrimethoxysilane,ethyltriethoxysilane, vinyltrimnethoxysilane, vinyltrichiorosilane,vinyltriacetoxysilane, vmnyltriethoxysilane,methoxyphenyltrimethoxysilane, mcthoxyphenyltriethoxysilane,methoxyphenyltriacetoxysilane, methoxyphenyltrichiorosilane,methoxybenzyltrimethoxysilane, methoxybenzyltriethoxysilane,methoxybenzyltriacetoxysilane, methoxybenzyltrichlorosilane,methoxyphenethyltrimethoxysilane, methoxyphenethyltriethoxysilane,methoxyphenetbyltriacetoxysilane, methoxyphenethyltrichlorosilane,ethoxyphenyltrimethoxysilane, etboxyphenyltriethoxysilane,ethoxyphenyltriacetoxysilane, ethoxyphenyltrichlorosilane,ethoxybenzyltrimethoxysilane, etboxybenzyltriethoxysilane,ethoxybenzyltriacetoxysilane, ethoxybenzyltrichlorosilane,isopropoxyphenyltrimethoxysilane, isopropoxyphenyltriethoxysilane,isopropoxyphenyltriacetoxysilane, isopropoxyphenyltrichlorosilane,isopropoxybenzyltrimetboxysilane, isopropoxybenzyltriethoxysilane,isopropoxybenzyltriacetoxysilane, isopropoxybenzyltrichlorosilane,t-butoxyphenyltrimethoxysilane, t-butoxyphenyltriethoxysilane,t-butoxyphenyltriacetoxysilane, t-butoxyphenyltrichlorosilane,t-butoxybenzyltrimethoxysilane, t-butoxybcnzyltriethoxysilane,t-butoxybenzyltriacetoxysilane, t-buoxybenzyltrichlorosilane,methoxynaphthyltrimetboxysilanc, methoxynaphthyltriethoxysilane,methoxynaphthyltriacetoxysilane, methoxynaphthyltrichlorosilane,ethoxynaphthyltrimethoxysilane, ethoxynaphthyltriethoxysilane,ethoxynaphthyltriacetoxysilane, ethoxynaphtbyltrichlorosilane,γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane,γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane,γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane,γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane,chloromethyltrimethoxysilane, chloromethyltriethoxysilane,dimethyldimethoxysilane, phenylmethyldimethoxysilane,dimethyldiethoxysilane, phenylmethyldiethoxysilane,γ-chloropropylmethyldimetboxysilane, γ-chloropropylmethyldiethoxysilane,dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimnethoxysilane,γ-methacryloxypropylmnethyldiethoxysilane,γ-mercaptopropylmethyldimnethoxysilane, γ-mercaptomnethyldiethoxysilane,methylvinyldimethoxysilane, and methylvinyldiethoxysilane.

The following hydrolyzable silanes can also be used.

Examples of the silicon-containing compound of Formula (4) includemethylenebistrimethoxysilane, methylenebistrichlorosilane,methylenebistriacetoxysilane, ethylenebistriethoxysilane,ethylenebistrichlorosilane, ethylenebistriacetoxysilane,propylenebistriethoxysilane, butylenebistrimethoxysilane,phenylenebistrimethoxysilane, phenylenebistriethoxysilane,phenylenebismethyldiethoxysilane, phenylenebismethyldimethoxysilane,naphthylenebistrimethoxysilane, bistrimethoxydisilane,bistriethoxydisilane, bisethyldiethoxydisilane, andbismethyldimethoxydisilane.

Specific examples of the hydrolysis condensate (polysiloxane) used inthe present invention are exemplified below.

The hydrolysis condensate (polyorganosiloxane) of the hydrolyzablesilane having a weight average molecular weight of 1,000 to 1,000,000,or 1,000 to 100,000 can be obtained. The molecular weight is a molecularweight obtained by GPC analysis in terms of polystyrene.

For example, measurement conditions of GPC are as follows: GPC equipment(trade name HLC-8220GPC, manufactured by Tosoh Co., Ltd), GPC column(trade name Shodex KF803L, KF802, and KF801, manufactured by Showa DenkoKK), Column temperature 40° C., Eluent (elution solvent)tetrahydrofuran, and Flow volume (flow rate) 1.0 ml/min. The measurementcan be carried out by using polystyrene (manufactured by Showa Denko KK)as a standard sample.

For hydrolysis of alkoxysilyl groups, acyloxysilyl groups, orhalogenated silyl groups, 0.5 mol to 100 mol, preferably 1 mol to 10 molof water per 1 mol of the hydrolyzable group is used.

A hydrolysis catalyst of 0.001 mol to 10 mol and preferably 0.001 mol to1 mol per 1 mol of the hydrolyzable group can be used.

The reaction temperature at the time of the hydrolysis and condensationis usually 20° C. to 80° C.

The hydrolysis may be complete hydrolysis or may be partial hydrolysis.In other words, a hydrolysis product and a monomer may remain in thehydrolysis condensate.

A catalyst may be used at the time of the hydrolysis and condensation.Examples of the hydrolysis catalyst include a metal chelate compound, anorganic acid, an inorganic acid, an organic base, and an inorganic base.

Examples of the metal chelate compound as the hydrolysis catalystinclude titanium chelate compounds such astriethoxy-mono(acetylacetonato) titanium,tri-n-propoxy-mono(acetylacetonato) titanium,tri-i-propoxy-mono(acetylacetonato) titanium,tri-n-butoxy-mono(acetylacetonato) titanium,tri-sec-butoxy-mono(acetylacetonato) titanium,tri-t-butoxy-mono(acetylacetonato) titanium,diethoxy-bis(acetylacetonato) titanium,di-n-propoxy-bis(acetylacetonato) titanium,di-i-propoxy-bis(acetylacetonato) titanium,di-n-butoxy-bis(acetylacetonato) titanium,di-sec-butoxy-bis(acetylacetonato) titanium,di-t-butoxy-bis(acetylacetonato) titanium,monoethoxy-tris(acetylacetonato) titanium,mono-n-propoxy-tris(acetylacetonato) titanium,mono-i-propoxy-tris(acetylacetonato) titanium,mono-n-butoxy-tris(acetylacetonato) titanium,mono-sec-butoxy-tris(acetylacetonato) titanium,mono-t-butoxy-tris(acetylacetonato) titanium, tetrakis(acetylacetonato)titanium, triethoxy-mono(ethyl acetoacetate) titanium,tri-n-propoxy-mono(ethyl acetoacetate) titanium,tri-i-propoxy-mono(ethyl acetoacetate) titanium, tri-n-butoxy-mono(ethylacetoacetate) titanium, tri-sec-butoxy-mono(ethyl acetoacetate)titanium, tri-t-butoxy-mono(ethyl acetoacetate) titanium,diethoxy-bis(ethyl acetoacetate) titanium, di-n-propoxy-bis(ethylacetoacetate) titanium, di-i-propoxy-bis(ethyl acetoacetate) titanium,di-n-butoxy-bis(ethyl acetoacetate) titanium, di-sec-butoxy-bis(ethylacetoacetate) titanium, di-t-butoxy-bis(ethyl acetoacetate) titanium,monoethoxy-tris(ethyl acetoacetate) titanium, mono-n-propoxy-tris(ethylacetoacetate) titanium, mono-i-propoxy-tris(ethyl acetoacetate)titanium, mono-n-butoxy-tris(ethyl acetoacetate) titanium,mono-sec-butoxy-tris(ethyl acetoacetate) titanium,mono-t-butoxy-tris(ethyl acetoacetate) titanium, tetrakis(ethylacetoacetate) titanium, mono(acetylacetonato)-tris(ethyl acetoacetate)titanium, bis (acetylacetonato)-bis(ethyl acetoacetate) titanium, andtris(acetylacetonato)-mono(ethyl acetoacetate) titanium; zirconiumchelate compounds such as triethoxy-mono(acetylacetonato) zirconium,tri-n-propoxy-mono(acetylacetonato) zirconium,tri-i-propoxy-mono(acetylacetonato) zirconium,tri-n-butoxy-mono(acetylacetonato) zirconium,tri-sec-butoxy-mono(acetylacetonato) zirconium,tri-t-butoxy-mono(acetylacetonato) zirconium,diethoxy-bis(acetylacetonato) zirconium,di-n-propoxy-bis(acetylacetonato) zirconium,di-i-propoxy-bis(acetylacetonato) zirconium,di-n-butoxy-bis(acetylacetonato) zirconium,di-sec-butoxy-bis(acetylacetonato) zirconium,di-t-butoxy-bis(acetylacetonato) zirconium,monoethoxy-tris(acetylacetonato) zirconium,mono-n-propoxy-tris(acetylacetonato) zirconium,mono-i-propoxy-tris(acetylacetonato) zirconium,mono-n-butoxy-tris(acetylacetonato) zirconium,mono-sec-butoxy-tris(acetylacetonato) zirconium,mono-t-butoxy-tris(acetylacetonato) zirconium, tetrakis(acetylacetonato)zirconium, triethoxy-mono(ethyl acetoacetate) zirconium,tri-n-propoxy-mono(ethyl acetoacetate) zirconium,tri-i-propoxy-mono(ethyl acetoacetate) zirconium,tri-n-butoxy-mono(ethyl acetoacetate) zirconium,tri-sec-butoxy-mono(ethyl acetoacetate) zirconium,tri-t-butoxy-mono(ethyl acetoacetate) zirconium, diethoxy-bis(ethylacetoacetate) zirconium, di-n-propoxy-bis(ethyl acetoacetate) zirconium,di-i-propoxy-bis(ethyl acetoacetate) zirconium, di-n-butoxy-bis(ethylacetoacetate) zirconium, di-sec-butoxy-bis(ethyl acetoacetate)zirconium, di-t-butoxy-bis(ethyl acetoacetate) zirconium,monoethoxy-tris(ethyl acetoacetate) zirconium, mono-n-propoxy-tris(ethylacetoacetate) zirconium, mono-i-propoxy-tris(ethyl acetoacetate)zirconium, mono-n-butoxy-tris(ethyl acetoacetate) zirconium,mono-sec-butoxy-tris(ethyl acetoacetate) zirconium,mono-t-butoxy-tris(ethyl acetoacetate) zirconium, tetrakis(ethylacetoacetate) zirconium, mono(acetylacetonato)-tris(ethyl acetoacetate)zirconium, bis(acetylacetonato)-bis(ethyl acetoacetate) zirconium, andtris(acetylacetonato)-mono(ethyl acetoacetate) zirconium; and aluminumchelate compounds such as tris(acetylacetonato) aluminum and tris(ethylacetoacetate) aluminum.

Examples of the organic acid as the hydrolysis catalyst include aceticacid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid,heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalicacid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallicacid, butyric acid, mellitic acid, arachidonic acid, 2-ethylhexanoicacid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylicacid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid,benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid,trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid,sulfonic acids, phthalic acid, fumaric acid, citric acid, and tartaricacid.

Examples of the inorganic acid as the hydrolysis catalyst includehydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, andphosphoric acid.

Examples of the organic base as the hydrolysis catalyst includepyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline,trimethylamine, triethylamine, monoethanolamine, diethanolamine,dimethyl-monoethanolamine, monomethyl-diethanolamine, triethanolamine,diazabicyclooctane, diazabicyclononane, diazabicycloundecene, andtetramethylammonium hydroxide. Examples of the inorganic base includeammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, andcalcium hydroxide. Among these catalysts, the metal chelate compound,the organic acid, and the inorganic acid are preferable, and thesecatalysts may be used singly or in combination of two or more of them.

Examples of the organic solvent used for the hydrolysis includealiphatic hydrocarbon solvents such as n-pentane, i-pentane, n-hexane,i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane,i-octane, cyclohexane, and methylcyclohexane; aromatic hydrocarbonsolvents such as benzene, toluene, xylene, ethylbenzene,trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene,diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene,n-amylnaphthalene, and trimethylbenzene; monoalcohol solvents such asmethanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol,sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol,sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol,sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol,2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4,n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecylalcohol, sec-heptadecyl alcohol, phenol, cyclohexanol,methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethyl carbinol, diacetone alcohol, and cresol; polyalcohol solventssuch as ethylene glycol, propylene glycol, 1,3-butylene glycol,pentanediol-2,4,2-methylpentanediol-2,4, hexanediol-2,5,heptanediol-2,4,2-ethylhexanediol-1,3, diethylene glycol, dipropyleneglycol, triethylene glycol, tripropylene glycol, and glycerin; ketonesolvents such as acetone, methylethyl ketone, methyl-n-propyl ketone,methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone,methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone,di-i-butyl ketone, trimethylnonanone, cyclohexanone,methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetonealcohol, acetophenone, and fenchone; ether solvents such as ethyl ether,i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether,ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyl-dioxolane,dioxane, dimethyl dioxane, ethylene glycol monomethyl ether, ethyleneglycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycolmono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycolmonophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethyleneglycol dibutyl ether, diethylene glycol monomethyl ether, diethyleneglycol monoethyl ether, diethylene glycol diethyl ether, diethyleneglycol mono-n-butyl ether, diethylene glycol di-n-butyl ether,diethylene glycol mono-n-hexyl ether, ethoxy triglycol, tetraethyleneglycol di-n-butyl ether, propylene glycol monomethyl ether, propyleneglycol monoethyl ether, propylene glycol monopropyl ether, propyleneglycol monobutyl ether, propylene glycol monomethyl ether acetate,dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether,dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether,tripropylene glycol monomethyl ether, tetrahydrofuran, and2-methyltetrahydrofuran; ester solvents such as diethyl carbonate,methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone,n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate,sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methxoybutylacetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexylacetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate,n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethyleneglycol monomethyl ether acetate, ethylene glycol monoethyl etheracetate, diethylene glycol monomethyl ether acetate, diethylene glycolmonoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate,propylene glycol monomethyl ether acetate, propylene glycol monoethylether acetate, propylene glycol monopropyl ether acetate, propyleneglycol monobutyl ether acetate, dipropylene glycol monomethyl etheracetate, dipropylene glycol monoethyl ether acetate, glycol di-acetate,methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amylpropionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyllactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethylphthalate, and diethyl phthalate; nitrogen-containing solvents such asN-methylformamide, N,N-dimethylformamide, N,N-diethylformamide,acetamide, N-methylacetamide, N,N-dimethylacetamide,N-methylpropionamide, and N-methylpyrrolidone; and sulfur-containingsolvents such as dimethyl sulfide, diethyl sulfide, thiophene,tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propanesultone. These solvents can be used singly or in combination of two ormore of them.

In particular, the following ketone solvents are preferable from theviewpoint of storage stability of the obtained solution: acetone,methylethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone,diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone,ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone,trimethyl nonanone, cyclohexanone, methylcyclohexanone,2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, andfenchone.

Bisphenol S or a bisphenol S derivative can be added as an additive. Thebisphenol S or the bisphenol S derivative is added in an amount of 0.01part by mass to 20 parts by mass, 0.01 part by mass to 10 parts by mass,or 0.01 part by mass to 5 parts by mass relative to 100 parts by mass ofthe polyorganosiloxane.

The preferable bisphenol S or bisphenol S derivatives are exemplifiedbelow.

The resist underlayer film forming composition for lithography of thepresent invention may contain a curing catalyst. The curing catalystacts as a curing catalyst when a coating film containing apolyorganosiloxane made of the hydrolysis condensate is heated andcured.

Examples of the usable curing catalyst include ammonium salts,phosphines, phosphonium salts, and sulfonium salts.

Examples of the ammonium salts include a quaternary ammonium salt havinga structure of Formula (D-1):

(wherein m is an integer of 2 to 11; n is an integer of 2 or 3; R²¹ isan alkyl group or an aryl group; and Y_(A) ⁻ is an anion),

a quaternary ammonium salt having a structure of Formula (D-2):

R²²R²³R²⁴R²⁵N⁺Y_(A) ⁻  Formula (D-2)

(wherein R²², R²³, R²⁴, and R²⁵ are alkyl groups or aryl groups; N is anitrogen atom, Y_(A) ⁻ is an anion; and R²², R²³, R²⁴, and R^(2S) eachare bonded to the nitrogen group through a C—N bond),

a quaternary ammonium salt having a structure of Formula (D-3):

(wherein R²⁶ and R²⁷ are alkyl groups or aryl groups, and Y_(A) ⁻ is ananion),

a quaternary ammonium salt having a structure of Formula (D-4):

(wherein R²⁸ is an alkyl group or an aryl group, and Y_(A) ⁻ is ananion),

a quaternary ammonium salt having a structure of Formula (D-5):

(wherein R²⁹ and R³⁰ are alkyl groups or aryl groups, and Y_(A) ⁻ is ananion), and

a tertiary ammonium salt having a structure of Formula (D-6):

(wherein m is an integer of 2 to 11; n is an integer of 2 or 3; H is ahydrogen atom; and Y_(A) ⁻ is an anion).

Examples of the phosphonium salts include a quaternary phosphonium saltof Formula (D-7):

R³¹R³²R³³R³⁴P⁺Y_(A) ⁻  Formula (D-7)

(wherein R³¹, R³², R³³, and R³⁴ are alkyl groups or aryl groups; P is aphosphorus atom; Y_(A) ⁻ is an anion, and R³¹, R³², R³³, and R³ each arebonded to the phosphorus atom through a C—P bond).

Examples of the sulfonium salts include a tertiary sulfonium salt ofFormula (D-8):

R³⁵R³⁶R³⁷S⁺Y_(A) ⁻  Formula (D-8)

(wherein R³⁵, R³⁶, and R³⁷ are alkyl groups or aryl groups; S is asulfur atom; Y_(A) ⁻ is an anion, and R³⁵, R³⁶, and R³⁷ each are bondedto the sulfur atom through a C—S bond).

The compound of Formula (D-1) is a quaternary ammonium salt derived froman amine. m is an integer of 2 to 11 and n is an integer of 2 or 3. R²¹in the quaternary ammonium salt is a C₁₋₁₈ alkyl group or aryl group andpreferably a C₂₋₁₀ alkyl group or aryl group. Examples of R²¹ includelinear alkyl groups such as ethyl group, propyl group, and butyl group;and benzyl group, cyclohexyl group, cyclohexylmethyl group, anddicyclopentadienyl group. Examples of the anion (Y_(A) ⁻) includehalogen ions such as chlorine ion (Cl⁻), bromide ion (Br⁻), and iodideion (I⁻), and acid groups such as carboxylate (—COO⁻), sulfonate (—SO₃⁻), and alcoholate (—O⁻).

The compound of Formula (D-2) is a quaternary ammonium salt ofR²²R²³R²⁴R²⁵N⁺Y_(A) ⁻. R²², R²³, R²⁴, and R²⁵ in the quaternary ammoniumsalt are C₁₋₁₈ alkyl groups or aryl groups, or silane compounds bondingto a silicon atom through a Si—C bond. Examples of the anion (Y_(A) ⁻)include halogen ions such as chlorine ion (Cl⁻), bromide ion (Br⁻), andiodide ion (I⁻), and acid groups such as carboxylate (—COO⁻), sulfonate(—SO₃ ⁻), and alcoholate (—O⁻). The quaternary ammonium salt iscommercially available and examples of the quaternary ammonium saltinclude tetramethylammonium acetate, tetrabutylammonium acetate,triethylbenzylammonium chloride, triethylbenzylammonium bromide,trioctylmethylammonium chloride, tributylbenzylammonium chloride, andtrimethylbenzylammonium chloride.

The compound of Formula (D-3) is a quaternary ammonium salt derived from1-substituted imidazole. R²⁶ and R²⁷ are C₁₋₁₈ alkyl groups or arylgroups. The total carbon atoms of R²⁶ and R²⁷ are preferably 7 or more.Examples of R²⁶ include methyl group, ethyl group, propyl group, phenylgroup, and benzyl group and examples of R²⁷ include benzyl group, octylgroup, and octadecyl group. Examples of the anion (Y_(A) ⁻) includehalogen ions such as chlorine ion (Cl⁻), bromide ion (Br⁻), and iodideion (I⁻), and acid groups such as carboxylate (—COO⁻), sulfonate (—SO₃⁻), and alcoholate (—O⁻). The compound is commercially available, or canbe produced by reacting, for example, an imidazole-based compound suchas 1-methylimidazole and 1-benzylimidazole with a halogenated alkyl or ahalogenated aryl such as benzyl bromide and methyl bromide.

The compound of Formula (D-4) is a quaternary ammonium salt derived frompyridine. R²⁸ is a C₁₋₁₈ alkyl group or aryl group and preferably aC₄₋₁₈ alkyl group or aryl group. Examples of R²⁸ include butyl group,octyl group, benzyl group, and lauryl group. Examples of the anion(Y_(A) ⁻) include halogen ions such as chlorine ion (Cl⁻), bromide ion(Br⁻), and iodide ion (I⁻), and acid groups such as carboxylate (—COO⁻),sulfonate (—SO₃ ⁻), and alcoholate (—O⁻). The compound is commerciallyavailable, or can be manufactured by reacting, for example, pyridinewith a halogenated alkyl or a halogenated aryl such as lauryl chloride,benzyl chloride, benzyl bromide, methyl bromide, and octyl bromide.Examples of the compound include N-laurylpyridinium chloride andN-benzylpyridinium bromide.

The compound of Formula (D-5) is a quaternary ammonium salt derived froma substituted pyridine as represented by picoline and the like. R²⁹ is aC₁₋₁₈ alkyl group or aryl group and preferably a C₄₋₁₈ alkyl group oraryl group. Examples of R²⁹ include methyl group, octyl group, laurylgroup, and benzyl group. R³⁰ is a C₁₋₁₈ alkyl group or aryl group. Forexample, R³⁰ is methyl group when the compound is a quaternary ammoniumderived from picoline. Examples of the anion (Y_(A) ⁻) include halogenions such as chlorine ion (Cl⁻), bromide ion (Br⁻), and iodide ion (I⁻),and acid groups such as carboxylate (—COO⁻), sulfonate (—SO₃ ⁻), andalcoholate (—O⁻). The compound is commercially available, or can bemanufactured by reacting, for example, a substituted pyridine such aspicoline with a halogenated alkyl or a halogenated aryl such as methylbromide, octyl bromide, lauryl chloride, benzyl chloride, and benzylbromide. Examples of the compound include N-bcnzylpicolinium chloride,N-benzylpicolinium bromide, and N-laurylpicolinium chloride.

The compound of Formula (D-6) is a tertiary ammonium salt derived froman amine. m is an integer of 2 to 11 and n is an integer of 2 or 3.Examples of the anion (Y_(A) ⁻) include halogen ions such as chlorineion (Cl⁻), bromide ion (Br⁻), and iodide ion (I⁻), and acid groups suchas carboxylate (—COO⁻), sulfonate (—SO₃ ⁻), and alcoholate (—O⁻). Thecompound can be produced by reacting an amine with a weak acid such as acarboxylic acid and phenol. Examples of the carboxylic acid includeformic acid and acetic acid. When formic acid is used, the anion (Y_(A)⁻) is (HCOO⁻), and when acetic acid is used, the anion (Y_(A) ⁻) is(CH₃COO⁻). When phenol is used, the anion (Y_(A) ⁻) is (C₆H₅O⁻).

The compound of Formula (D-7) is a quaternary phosphonium salt having astructure of R³¹R³²R³³R³⁴P⁺Y_(A) ⁻. R³¹, R³², R³³, and R³⁴ are C₁₋₁₈alkyl groups or aryl groups, or silane compounds bonding to a siliconatom through a Si—C bond. Preferably three out of the four substituentsof R³¹ to R³⁴ are phenyl groups or substituted phenyl groups, andexamples of the phenyl group or substituted phenyl group include phenylgroup and tolyl group. Remaining one substituent is a C₁₋₁₈ alkyl group,an aryl group, or a silane compound bonding to a silicon atom through aSi—C bond. Examples of the anion (Y_(A) ⁻) include halogen ions such aschlorine ion (Cl⁻), bromide ion (Br⁻), and iodide ion (I⁻), and acidgroups such as carboxylate (—COO⁻), sulfonate (—SO₃ ⁻), and alcoholate(—O⁻). The compound is commercially available and examples of thecompound include halogenated tetraalkylphosphoniums such as halogenatedtetra-n-butylphosphoniums and halogenated tetra-n-propylphosphoniums;halogenated trialkylbenzylphosphoniums such as halogenatedtriethylbenzylphosphoniums; halogenated triphenyl-mono-alkylphosphoniumssuch as halogenated triphenylmethylphosphoniums and halogenatedtriphenylethylphosphoniums; halogenated triphenylbenzylphosphoniums,halogenated tetraphenylphosphoniums, halogenatedtritolyl-mono-arylphosphoniums, and halogenatedtritolyl-mono-alkylphosphoniums (the halogen atom is a chlorine atom ora bromine atom). Particularly preferable examples include halogenatedtriphenyl-mono-alkylphosphoniums such as halogenatedtriphenylmethylphosphoniums and halogenated triphenylethylphosphoniums;halogenated triphenyl-mono-arylphosphoniums such as halogenatedtriphenylbenzylphosphoniums; halogenated tritolyl-mono-arylphosphoniumssuch as halogenated tritolyl-mono-phenylphosphoniums; and halogenatedtritolyl-mono-alkylphosphoniums such as halogenatedtritolyl-mono-methylphosphoniums (the halogen atom is a chlorine atom ora bromine atom).

Examples of the phosphines include primary phosphines such asmethylphosphine, ethylphosphine, propylphosphine, isopropylphosphine,isobutylphosphine, and phenylphosphine; secondary phosphines such asdimethylphosphine, diethylphosphine, diisopropylphosphine,diisoamylphosphine, and diphenylphosphine; and tertiary phosphines suchas trimethylphosphine, triethylphosphine, triphenylphosphine,methyldiphenylphosphine, and dimethylphenylphosphine.

The compound of Formula (D-8) is a tertiary sulfonium salts having astructure of R³⁵R³⁶R³⁷S⁺Y_(A) ⁻. R³⁵, R³⁶, and R³⁷ are C₁₋₁₈ alkylgroups or aryl groups, or silane compounds bonding to a silicon atomthrough a Si—C bond. Preferably three out of the four substituents ofR³⁵ to R³⁷ are phenyl groups or substituted phenyl groups, and examplesof the phenyl groups or substituted phenyl groups include phenyl groupand tolyl group. Remaining one substituent is a C₁₋₁₈ alkyl group or anaryl group. Examples of the anion (Y_(A) ⁻) include halogen ions such aschlorine ion (Cl⁻), bromide ion (Br⁻), and iodide ion (I⁻), and acidgroups such as carboxylate (—COO⁻), sulfonate (—SO₃ ⁻), alcoholate(—O⁻), maleic acid anion, and nitric acid anion. The compound iscommercially available and examples of the compound include halogenatedtetraalkylsulfoniums such as halogenated tri-n-butylsulfoniums andhalogenated tri-n-propylsulfoniums; halogenated trialkylbenzylsulfoniumssuch as halogenated diethylbenzylsulfoniums; halogenateddiphenyl-mono-alkyl sulfoniums such as halogenateddiphenylmethylsulfoniums and halogenated diphenylethylsulfoniums;halogenated triphenylsulfoniums (the halogen atom is a chlorine atom orbromine atom), tetraalkylphosphonium carboxylates such astri-n-butylsulfonium carboxylate and tri-n-propylsulfonium carboxylate;trialkylbenzylsulfonium carboxylates such as diethylbenzylsulfoniumcarboxylate; diphenyl-mono-alkylsulfonium carboxylates such asdiphenylmethylsulfonium carboxylate and diphenylethylsulfoniumcarboxylate; and triphenylsulfonium carboxylate. The halogenatedtriphenylsulfonium and the triphenylsulfonium carboxylate are preferablyused.

In the present invention, a nitrogen-containing silane compound can beadded as the curing catalyst. Examples of the nitrogen-containing silanecompound include imidazole ring-containing silane compounds such asN-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.

The amount of the curing catalyst is 0.01 part by mass to 10 parts bymass, 0.01 part by mass to 5 parts by mass, or 0.01 part by mass to 3parts by mass relative to 100 parts by mass of the polyorganosiloxane.

The hydrolyzable silane is hydrolyzed and condensed in the solvent usingthe catalyst. From the obtained mixture of hydrolysis condensate (apolymer), alcohols as by-products and the hydrolysis catalyst and waterused can be simultaneously removed by distillation under reducedpressure or other operations. The acid catalyst and the base catalystused for the hydrolysis can be removed by neutralization or ionexchange.

To the resist underlayer film forming composition for lithography of thepresent invention, an organic acid, water, an alcohol, or a combinationthereof can be added in order to stabilize the resist underlayer filmforming composition having the hydrolysis condensate.

Examples of the organic acid include oxalic acid, malonic acid,methylmalonic acid, succinic acid, maleic acid, malic acid, tartaricacid, phthalic acid, citric acid, glutaric acid, citric acid, lacticacid, and salicylic acid. Among them, oxalic acid, maleic acid, and thelike are preferable. The amount of the organic acid to be added is 0.1part by mass to 5.0 parts by mass relative to 100 parts by mass of thecondensate (polyorganosiloxane). As the water to be added, pure water,ultrapure water, ion-exchanged water, and the like can be used. Theamount of the water to be added can be 1 part by mass to 20 parts bymass relative to 100 parts by mass of the resist underlayer film formingcomposition.

As the alcohol to be added, an alcohol that is easy to be evaporated byheating after application is preferable. Examples of the alcohol includemethanol, ethanol, propanol, isopropanol, and butanol. The amount of thealcohol to be added can be 1 part by mass 20 to 20 parts by massrelative to 100 parts by mass of the resist underlayer film formingcomposition.

In addition to the above components, the underlayer film formingcomposition for lithography of the present invention may contain, forexample, an organic polymer compound, an photoacid generator, and asurfactant, if necessary.

Use of the organic polymer compound allows a dry etching rate (adecreased amount in film thickness per unit time), an attenuationcoefficient, and a refractive index of the resist underlayer film formedfrom the underlayer film forming composition for lithography of thepresent invention to be adjusted.

The organic polymer compound is not particularly limited and variousorganic polymers can be used. Condensation polymerization polymers andaddition polymerization polymers, and the like can be used. The additionpolymerization polymers and the condensation polymerization polymerssuch as polyesters, polystyrenes, polyimides, acrylic polymers,methacrylic polymers, polyvinyl ethers, phenol novolacs, naphtholnovolacs, polyether, polyamides, and polycarbonates can be used. Organicpolymers having an aromatic ring structure such as a benzene ring, anaphthalene ring, an anthracene ring, a triazine ring, a quinoline ring,and a quinoxaline ring that function as a light absorbing moiety arepreferably used.

In the case where the organic polymer compound contains hydroxy groups,these hydroxy groups can form a crosslinking reaction with thepolyorganosiloxane.

As the organic polymer compound, the polymer compound having a weightaverage molecular weight of, for example, 1,000 to 1,000,000, 3,000 to300,000, 5,000 to 200,000, or 10,000 to 100,000 can be used.

The organic polymer compounds can be used singly or in combination oftwo or more of them.

When the organic polymer compound is used, a ratio of the organicpolymer compound is 1 part by mass to 200 parts by mass, 5 parts by massto 100 parts by mass, 10 parts by mass to 50 parts by mass, or 20 partsby mass to 30 parts by mass relative to 100 parts by mass of thecondensate (polyorganosiloxane).

The resist underlayer film forming composition for lithography of thepresent invention may contain an acid generator.

Examples of the acid generator include a thermal acid generator and aphotoacid generator.

The photoacid generator generates an acid at the time of exposure of theresist. Therefore, the acidity of the underlayer film can be adjusted.This is one method for adjusting the acidity of the underlayer film tothe acidity of the resist of the upper layer. The pattern shape of theresist formed on the upper layer can be controlled by adjusting theacidity of the underlayer film.

Examples of the photoacid generator contained in the resist underlayerfilm forming composition of the present invention include onium saltcompounds, sulfonimide compounds, and disulfonyldiazomethane compounds.

Examples of the onium salt compounds include iodonium salt compoundssuch as diphenyliodonium hexafluorophosphate, diphenyliodoniumtrifluoromethanesulfonate, diphenyliodoniumnonafluoro-normal-butanesulfonate, diphenyliodoniumperfluoro-normal-octanesulfonate, diphenyliodonium camphorsulfonate,bis(4-tert-butylphenyl)iodonium camphorsulfonate, andbis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; and sulfoniumsalt compounds such as triphenylsulfonium hexafluoroantimonate,triphenylsulfonium nonafluoro-normal-butanesulfonate, triphenylsulfoniumcamphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

Examples of the sulfonimide compound includeN-(trifluoromethanesulfonyloxy)succinimide,N-(nonafluoro-normal-butanesulfonyloxy)succinimide,N-(camphorsulfonyloxy)succinimide, andN-(trifluoromethanesulfonyloxy)naphthalimide.

Examples of the disulfonyldiazomethane compound includebis(trifluoromethylsulfonyl)diazomethane,bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane,bis(p-toluenesulfonyl)diazomethane,bis(2,4-dimethylbenzenesulfonyl)diazomethane, andmethylsulfonyl-p-toluenesulfonyldiazomethane.

The photoacid generator can be used singly or can be used in combinationof two or more of them.

When the photoacid generator is used, a ratio thereof is 0.01 part bymass to 15 parts by mass, 0.1 part by mass to 10 parts by mass, or 0.5part by mass to 1 part by mass relative to 100 parts by mass of thecondensate (polyorganosiloxane).

A surfactant is effective for reducing generation of pinholes andstriations when the resist underlayer film forming composition forlithography of the present invention is applied to the substrate.

Examples of the surfactant contained in the resist underlayer filmforming composition of the present invention include nonionicsurfactants such as polyoxyethylene alkyl ethers such as polyoxyethylenelauryl ethers, polyoxyethylene stearyl ethers, polyoxyethylene cetylethers, and polyoxyethylene oleyl ethers; polyoxyethylene alkylarylethers such as polyoxyethylene octylphenol ethers and polyoxyethylenenonylphenol ethers; polyoxyethylene-polyoxypropylene block copolymers;sorbitan fatty acid esters such as sorbitan monolaurates, sorbitanmonopalmitates, sorbitan monostearates, sorbitan monooleates, sorbitantrioleates, and sorbitan tristearates; and polyoxyethylene sorbitanfatty acid esters such as polyoxyethylene sorbitan monolaurates,polyoxyethylene sorbitan monopalmitates, polyoxyethylene sorbitanmonostearates, polyoxyethylene sorbitan trioleates, and polyoxyethylenesorbitan tristearates; fluorochemical surfactants such as Eftop EF301,EF303, and EF352 (trade name, manufactured by TOHKEM PRODUCTSCORPORATION), Megafac F171, F173, R-08, R-30, R-30N, and R-40LM (tradename, manufactured by DIC Corporation), Fluorad FC430 and FC431(manufactured by Sumitomo 3M Ltd.), Asahi guard AG710, Surflon S-382,SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by AsahiGlass Co., Ltd.); and Organosiloxane Polymer KP341 (manufactured byShin-Etsu Chemical Co., Ltd.). These surfactants can be used singly orcan be used in combination of two or more of them. When the surfactantis used, the ratio of the surfactant is 0.0001 part by mass to 5 partsby mass, 0.001 part by mass to 1 part by mass, or 0.01 part by mass to 1part by mass relative to 100 parts by mass of the condensate(polyorganosiloxane).

The resist underlayer film forming composition for lithography of thepresent invention can also contain, for example, a rheology modifier andan adhesion assistance agent. The rheology modifier is effective forimproving flowability of the underlayer film forming composition. Theadhesion assistance agent is effective for improving adhesion of theunderlayer film with the semiconductor substrate or the resist.

As a solvent used for the resist underlayer film forming composition forlithography of the present invention, any solvent can be used withoutlimitation as long as the solvent can dissolve the solid content.Examples of the solvent include methylcellosolve acetate,ethylcellosolve acetate, propylene glycol, propylene glycol monomethylether, propylene glycol monoethyl ether, methyl isobutyl carbinol,propylene glycol monobutyl ether, propylene glycol monomethyl etheracetate, propylene glycol monoethyl ether acetate, propylene glycolmonopropyl ether acetate, propylene glycol monobutyl ether acetate,toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone,ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methyl propionate, ethylethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate,methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethylpyruvate, ethylene glycol monomethyl ether, ethylene glycol monoethylether, ethylene glycol monopropyl ether, ethylene glycol monobutylether, ethylene glycol monomethyl ether acetate, ethylene glycolmonoethyl ether acetate, ethylene glycol monopropyl ether acetate,ethylene glycol monobutyl ether acetate, diethylene glycol dimethylether, diethylene glycol diethyl ether, diethylene glycol dipropylether, diethylene glycol dibutyl ether propylene glycol monomethylether, propylene glycol dimethyl ether, propylene glycol diethyl ether,propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyllactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyllactate, methyl formate, ethyl formate, propyl formate, isopropylformate, butyl formate, isobutyl formate, amyl formate, isoamyl formate,methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexylacetate, methyl propionate, ethyl propionate, propyl propionate,isopropyl propionate, butyl propionate, isobutyl propionate, methylbutyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butylbutyrate, isobutyl butyrate, ethyl hydroxyacetate, ethyl2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate,methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethylethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate,ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methoxypropylacetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate,toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butylketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone,N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide,N-methylpyrrolidone, 4-methyl-2-pentanol, and γ-butyrolactone. Thesesolvents can be used singly or in combination of two or more of them.

Hereinafter, the use of the resist underlayer film forming compositionfor lithography of the present invention will be described.

In order to process a substrate using the resist underlayer film formingcomposition of the present invention, a resist underlayer film is formedon the substrate by a coating method or a resist underlayer film isformed through an organic underlayer film on the substrate by thecoating method, and a resist film (for example, a photoresist, anelectron beam resist, or an EUV resist) is formed on the resistunderlayer film. Thereafter, a resist pattern is formed by exposure anddevelopment and the pattern is transferred by dry-etching the resistunderlayer film using the resist pattern. The substrate is processedusing the pattern or the pattern is transferred by etching the organicunderlayer film and the substrate is processed using the organicunderlayer film.

For forming a fine pattern, the thickness of the resist film tends tobecome thin in order to prevent pattern collapse. In the dry etching fortransferring the pattern to a film existing at the underlayer, thepattern cannot be transferred unless the etching rate is higher thanthat of the upper layer film due to the thinning of the resist. In thisrespect, the resist underlayer film formed from the resist underlayerfilm forming composition for lithography of the present invention has ahigher dry etching rate than that of the resist.

In the present invention, the substrate is coated with the resistunderlayer film (containing an inorganic silicon-based compound)according to the present invention through the organic underlayer filmor not through the organic underlayer film and the resist underlayerfilm is coated with the resist film (an organic resist film) in thisorder. Generally, the dry etching rate of the film formed of organiccomponents and the dry etching rate of the film formed of inorganiccomponents are significantly different depending on the selection of theetching gas. The film formed of the organic components has a higher dryetching rate when an oxygen-based gas is used, whereas the film formedof the inorganic components has a higher dry etching rate when ahalogen-containing gas is used.

Accordingly, for example, the resist pattern is formed, the resistunderlayer film according to the present invention existing at theunderlayer of the resist is dry-etched with the halogen-containing gasto transfer the pattern to the resist underlayer film, and the substrateis processed with the halogen-containing gas using the patterntransferred to the resist underlayer film. Alternatively, the pattern istransferred by dry-etching the organic underlayer film at the underlayerof the resist underlayer film with the oxygen-based gas using thepattern-transferred resist underlayer film and the substrate isprocessed with the halogen-containing gas using the pattern-transferredorganic underlayer film.

Hereinafter, the use will be described in more detail.

The resist underlayer film is formed by applying the resist underlayerfilm forming composition of the present invention onto the substrate(for example, a silicon wafer substrate, a silicon/silicon dioxidecoated substrate, a silicon nitride substrate, a glass substrate, an ITOsubstrate, a polyimide substrate, and a low dielectric constant material(low-k material) coated substrate) used in the production ofsemiconductor devices by an appropriate coating method such as a spinneror a coater and thereafter baking the applied composition. The bakingconditions are appropriately selected from a baking temperature of 80°C. to 250° C. and a baking time of 0.3 minute to 60 minutes. Thepreferable conditions are a baking temperature of 150° C. to 250° C. anda baking time of 0.5 minute to 2 minutes. The film thickness of theunderlayer film to be formed is, for example, 10 nm to 1,000 nm, 20 nmto 500 nm, 50 nm to 300 nm, or 100 nm to 200 nm.

Subsequently, for example, the layer of a photoresist is formed on theresist underlayer film. The photoresist layer can be formed by a knownmethod, that is, applying a photoresist composition solution onto theunderlayer film and baking the applied composition. The thickness of thephotoresist is, for example, 50 nm to 10,000 nm, 100 nm to 2,000 nm, or200 nm to 1,000 nm.

In the present invention, after the organic underlayer film is formed onthe substrate, the resist underlayer film of the present invention isformed on the organic underlayer film and a photoresist can be furtherformed on the resist underlayer film. Therefore, even when a photoresistpattern has a narrow width and the photoresist is thinly applied inorder to prevent the pattern collapse, the substrate can be processed byappropriately selecting an etching gas. For example, the resistunderlayer film of the present invention can be processed by using afluorine-based gas, which has a sufficiently higher etching rate thanthat of the photoresist, as the etching gas. The organic underlayer filmcan be processed by using the oxygen-based gas, which has a sufficientlyhigher etching rate than that of the resist underlayer film of thepresent invention, as the etching gas. The substrate can be processed byusing the fluorine-based gas, which has a sufficiently higher etchingrate than that of the organic underlayer film, as the etching gas.

The photoresist formed on the resist underlayer film of the presentinvention is not limited as long as the photoresist is sensitive to thelight used for exposure. Both negative type photoresists and positivetype photoresists can be used. Examples of the photoresist include apositive type photoresist made of a novolac resin and1,2-naphthoquinonediazide sulfonic acid ester, a chemically amplifiedphotoresist made of a binder having a group decomposed with an acid toincrease an alkali dissolution rate and a photoacid generator, achemically amplified photoresist made of a low molecular compounddecomposed with an acid to increase an alkali dissolution rate of thephotoresist, an alkali-soluble binder, and a photoacid generator, and achemically amplified photoresist made of a binder having a groupdecomposed with an acid to increase an alkali dissolution rate, a lowmolecular compound decomposed with an acid to increase an alkalidissolution rate of the photoresist, and a photoacid generator. Examplesof commercially available photoresists include APEX-E (trade name,manufactured by Shipley Company L.L.C.), PAR710 (trade name,manufactured by Sumitomo Chemical Company, Limited), and SEPR430 (tradename, manufactured by Shin-Etsu Chemical Co., Ltd.). In addition,fluorine atom-containing polymer-based photoresists as described inProc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364(2000), and Proc. SPIE, Vol. 3999, 365-374 (2000) can be included.

Subsequently, exposure to light is carried out through the predeterminedmask. A KrF excimer laser (a wavelength of 248 nm), an ArF excimer laser(a wavelength of 193 nm), an F₂ excimer laser (a wavelength of 157 nm),EUV, and the like can be used for the exposure. After exposure, postexposure bake can be carried out, if necessary. The post exposure bakingis carried out under appropriately selected conditions of a heatingtemperature of 70° C. to 150° C. and a heating time of 0.3 minute to 10minutes.

In the present invention, a resist for electron beam lithography or aresist for EUV lithography can be used as a resist instead of thephotoresist. Both negative type electron beam resists and positive typeelectron beam resists can be used. Examples of the electron beam resistinclude a chemically amplified resist made of an acid generator and abinder having a group decomposed with an acid to change an alkalidissolution rate, a chemically amplified resist made of an alkalisoluble binder, an acid generator, and a low molecular compounddecomposed with an acid to change an alkali dissolution rate of theresist, a chemically amplified resist made of an acid generator, abinder having a group decomposed with an acid to change an alkalidissolution rate, and a low molecular compound decomposed with an acidto change an alkali dissolution rate of the resist, a non-chemicallyamplified resist made of a binder having a group decomposed withelectron beams to change an alkali dissolution rate, and anon-chemically amplified resist made of a binder having a moiety that iscut by electron beams to change the alkali dissolution rate. When theseelectron beam resists are used, similar to the case where photoresist isused, a resist pattern can be formed by using electron beams as anirradiation source.

As the EUV resist, a methacrylate resin-based resist, amethacrylate-polyhydroxystyrene hybrid resin-based resist, and apolyhydroxystyrene resin-based resist can be used. Both a negative typeEUV resist and a positive type EUV resist can be used. Examples of theEUV resist include a chemically amplified resist made of an acidgenerator and a binder having a group decomposed with an acid to changean alkali dissolution rate, a chemically amplified resist made of analkali soluble binder, an acid generator, and a low molecular compounddecomposed with an acid to change an alkali dissolution rate of theresist, a chemically amplified resist made of an acid generator, abinder having a group decomposed with an acid to change an alkalidissolution rate, and a low molecular compound decomposed with an acidto change an alkali dissolution rate of the resist, a non-chemicallyamplified resist made of a binder having a group decomposed with EUVlight to change an alkali dissolution rate, and a non-chemicallyamplified resist made of a binder having a moiety that is cut by EUVlight to change the alkali dissolution rate.

Subsequently, development is carried out with a development solution(for example, an alkali development solution). This allows an exposedpart of the photoresist to be removed to form a pattern of thephotoresist when, for example, a positive type photoresist is used.Examples of the development solution include aqueous alkali solutionsincluding aqueous solutions of alkali metal hydroxides such as potassiumhydroxide and sodium hydroxide, aqueous solutions of quaternary ammoniumhydroxides such as tetramethylammonium hydroxide, tetraethylammoniumhydroxide, and choline, and aqueous solutions of amines such asethanolamine, propylamine, and ethylenediamine. In addition, asurfactant and the like can be added to the development solution. Thedevelopment conditions are appropriately selected from a temperature of5° C. to 50° C. and a time of 10 seconds to 600 seconds.

In the present invention, organic solvents can be used as thedevelopment solution. After exposure to light, development is carriedout with a development solution (a solvent). This allows an unexposedpart of the photoresist to be removed to form a pattern of thephotoresist when, for example, a positive type photoresist is used.

Examples of the development solution include methyl acetate, butylacetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamylacetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycolmonomethyl ether acetate, ethylene glycol monoethyl ether acetate,ethylene glycol monopropyl ether acetate, ethylene glycol monobutylether acetate, ethylene glycol monophenyl ether acetate, ethylene glycolmonobutyl ether acetate, ethylene glycol monophenyl ether acetate,diethylene glycol monomethyl ether acetate, diethylene glycol monopropylether acetate, diethylene glycol monoethyl ether acetate, diethyleneglycol monophenyl ether acetate, diethylene glycol monobutyl etheracetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutylacetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutylacetate, propylene glycol monoethyl ether acetate, propylene glycolmonopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate,4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentylacetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate,3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate,4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methylformate, ethyl formate, butyl formate, propyl formate, ethyl lactate,butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butylcarbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butylpyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate,ethyl propionate, propyl propionate, isopropyl propionate, methyl2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl3-methoxypropionate, ethyl 3-methoxypropionate, ethyl3-ethoxypropionate, and propyl 3-methoxypropionate. In addition, asurfactant and the like can be added to the development solution. Thedevelopment conditions are appropriately selected from a temperature of5° C. to 50° C. and a time of 10 seconds to 600 seconds.

After patterning the photoresist film by development, the part of theresist underlayer film (intermediate layer) of the present invention,where the photoresist film (upper layer) is removed, is removed by dryetching to expose the substrate. Examples of gases to be used for dryetching of the resist underlayer film of the present invention includetetrafluoromethane (CF₄), trifluoromethane (CHF₃), perfluorocyclobutane(C₄F₈), perfluoropropane (C₃F₈), trifluoromethane, carbon monoxide,argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogentrifluoride and chlorine trifluoride, chlorine, and trichloroborane anddichloroborane. For the dry etching of the resist underlayer film, it ispreferable to use the halogen-based gas. The photoresist made of organicsubstances is basically difficult to be removed by dry etching using thehalogen-based gas. On the contrary, the resist underlayer film of thepresent invention that contains many silicon atoms is rapidly removed bythe halogen-based gas. Therefore, reduction in the film thickness of thephotoresist film associated with the dry etching of the resistunderlayer film can be reduced. As a result, the photoresist can be usedas a thin film.

Dry etching of the resist underlayer film is preferably carried out by afluorine-based gas. Examples of the fluorine-based gas includetetrafluoromethane (CF₄), trifluoromethane (CHF₃), perfluorocyclobutane(C₄F₈), perfluoropropane (C₃F₈), trifluoromethane, and difluoromethane(CH₂F₂).

Subsequently, the semiconductor substrate is processed. Thesemiconductor substrate is preferably processed by dry etching with afluorine-based gas. Examples of the fluorine-based gas includetetrafluoromethane (CF₄), trifluoromethane (CHF₃), perfluorocyclobutane(C₄F₈), perfluoropropane (C₃F₈), trifluoromethane, and difluoromethane(CH₂F₂).

When the organic underlayer film is formed on the substrate, the resistunderlayer film (intermediate layer) of the present invention is removedusing the thus formed pattern of photoresist film (upper layer) as aprotection film. Subsequently, the organic underlayer film (underlayer)is removed using the patterned photoresist film (upper layer) and theresist underlayer film (intermediate layer) of the present invention asprotection films. Finally, the semiconductor substrate is processedusing the patterned resist underlayer film (intermediate layer) of thepresent invention and organic underlayer film (underlayer) as protectionfilms.

More specifically, first, the part of the resist underlayer film(intermediate layer) of the present invention, where the photoresistfilm (upper layer) is removed, is removed by dry etching using the abovemethod to expose the organic underlayer film (underlayer). Thereafter,the organic underlayer film is removed using the patterned photoresistfilm and film made of the resist underlayer film of the presentinvention as the protection films. The organic underlayer film(underlayer) is preferably dry-etched by using the oxygen-based gas.This is because the resist underlayer film of the present invention thatcontains many silicon atoms is difficult to be removed by dry etchingwith the oxygen-based gas.

Finally, the semiconductor substrate is processed. As described above,the semiconductor substrate is preferably processed by dry etching withthe fluorine-based gas.

An organic anti-reflective coating can be formed at the upper layer ofthe resist underlayer film of the present invention before forming thephotoresist film. The anti-reflective coating composition to be used isnot particularly limited and can be arbitrarily selected fromconventionally used anti-reflective coating compositions in lithographicprocesses. The anti-reflective coating can be formed by a conventionallyused method, that is, a method for applying the composition by, forexample, a spinner or a coater and baking the applied composition.

The substrate onto which the resist underlayer film forming compositionof the present invention is applied may have an organic or inorganicanti-reflective coating formed on the surface of the substrate by a CVDmethod or the like. The underlayer film of the invention may also beformed on the anti-reflective coating.

The resist underlayer film formed from the resist underlayer filmforming composition of the present invention may exhibit lightabsorption depending on the wavelength of light used in the lithographyprocess. In such a case, the resist underlayer film functions as ananti-reflective coating having an effect of preventing reflected lightfrom the substrate. The underlayer film of the present invention can beused as a layer for preventing interaction between the substrate and thephotoresist, a layer having a function of preventing an adverse effectof materials used for the photoresist or substances generated at thetime of exposure to the photoresist on a substrate, a layer having afunction of preventing diffusion of substances generated from thesubstrate at the time of heating and baking into the upper layerphotoresist, and a barrier layer for reducing the poisoning effect onthe photoresist layer due to the semiconductor substrate dielectriclayer.

The resist underlayer film formed from the resist underlayer filmforming composition of the present invention is applicable to asubstrate in which via holes used in a dual damascene process are formedand can be used as an embedding material capable of filling holeswithout gaps. The resist underlayer film composition can also be used asa planarizing material for planarizing the surface of a semiconductorsubstrate having unevenness.

In addition to the function as a hard mask, the resist underlayer filmas the underlayer film of the EUV resist can also be used for thefollowing object. The resist underlayer film forming composition can beused as an underlayer anti-reflective coating of the EUV resist, inwhich the underlayer anti-reflective coating does not cause intermixingwith the EUV resist and can prevent reflection of undesirable exposurelight such as UV or DUV (ArF light, KrF light) from the substrate orinterface at the time of EUV exposure (wavelength 13.5 nm). The resistunderlayer film can efficiently prevent reflection at the underlayer ofthe EUV resist. When the resist underlayer film is used for the EUVresist underlayer film, the process can be carried out in a similarmanner to the process for the underlayer film for the photoresist.

EXAMPLES Synthesis Example 1

Into a 300 ml flask, 24.93 g (70 mol %) of tetraethoxysilane, 1.70 g (5mol %) of phenyltrimethoxysilane, 6.10 g (20 mol %) oftriethoxymethylsilane, 2.71 g (5 mol %) oftrifluoroacetamidopropyltriethoxysilane, and 53.16 g of acetone werepoured and 11.40 g of 0.01 mol/1 hydrochloric acid was added dropwise tothe mixed solution with stirring the mixed solution using a magneticstirrer. After the addition, the flask was transferred to an oil bathcontrolled to 85° C. and the solution was reacted under heating refluxfor 240 minutes. Thereafter, the reaction solution was cooled to roomtemperature. To the reaction solution, 70.00 g of propylene glycolmonomethyl ether acetate was added. Methanol, ethanol, acetone, water,and hydrochloric acid as reaction byproducts were distilled off underreduced pressure and the reaction solution was concentrated to give thepropylene glycol monomethyl ether acetate solution of a hydrolysiscondensate (polymer). To the solution, propylene glycol monoethyl etherwas added so that the solution had a concentration of 20% by mass interms of solid residue at 140° C. in a solvent ratio of propylene glycolmonomethyl ether acetate/propylene glycol monoethyl ether of 20/80. Theobtained polymer corresponded to Formula (2-1) and the weight averagemolecular weight Mw of the polymer measured with GPC in terms ofpolystyrene was 1,800.

Synthesis Example 2

Into a 300 ml flask, 26.04 g (70 mol %) of tetraethoxysilane, 6.37 g (20mol %) of triethoxymethylsilane, 2.83 g (5 mol %) oftrifluoroacetamidopropyltriethoxysilane, 2.16 g (5 mol %) of4-methoxybenzyltrimethoxysilane, and 52.86 g of acetone were poured and11.90 g of 0.01 mol/l hydrochloric acid was added dropwise to the mixedsolution with stirring the mixed solution using a magnetic stirrer.After the addition, the flask was transferred to an oil bath controlledto 85° C. and the solution was reacted under heating reflux for 240minutes. Thereafter, the reaction solution was cooled to roomtemperature. To the reaction solution, 70.00 g of propylene glycolmonomethyl ether acetate was added. Methanol, ethanol, acetone, water,and hydrochloric acid as reaction byproducts were distilled off underreduced pressure and the reaction solution was concentrated to give thepropylene glycol monomethyl ether acetate solution of a hydrolysiscondensate (polymer). To the solution, propylene glycol monoethyl etherwas added so that the solution had a concentration of 20% by mass interms of solid residue at 140° C. in a solvent ratio of propylene glycolmonomethyl ether acetate/propylene glycol monoethyl ether of 20/80. Theobtained polymer corresponded to Formula (2-2) and the weight averagemolecular weight Mw of the polymer measured with GPC in terms ofpolystyrene was 1,600.

Synthesis Example 3

Into a 300 ml flask, 24.43 g (70 mol %) of tetraethoxysilane, 1.66 g (5mol %) of phenyltrimethoxysilane, 3.88 g (13 mol %) oftriethoxymethylsilane, 2.66 g (5 mol %) oftrifluoroacetamidopropyltriethoxysilane, 0.81 g (2 mol %) of4-methoxybenzyltrimethoxysilane, 2.90 g (5 mol %) ofphenylsulfonylpropyltriethoxysilane, and 53.30 g acetone were poured and11.17 g of 0.01 mol/1 hydrochloric acid was added dropwise to the mixedsolution with stirring the mixed solution using a magnetic stirrer.After the addition, the flask was transferred to an oil bath controlledto 85° C. and the solution was reacted under heating reflux for 240minutes. Thereafter, the reaction solution was cooled to roomtemperature. To the reaction solution, 70.00 g of propylene glycolmonomethyl ether acetate was added. Methanol, ethanol, acetone, water,and hydrochloric acid as reaction byproducts were distilled off underreduced pressure and the reaction solution was concentrated to give thepropylene glycol monomethyl ether acetate solution of a hydrolysiscondensate (polymer). To the solution, propylene glycol monoethyl etherwas added so that the solution had a concentration of 20% by mass interms of solid residue at 140° C. in a solvent ratio of propylene glycolmonomethyl ether acetate/propylene glycol monoethyl ether of 20/80. Theobtained polymer corresponded to Formula (2-3) and the weight averagemolecular weight Mw of the polymer measured with GPC in terms ofpolystyrene was 1,800.

Synthesis Example 4

Into a 300 ml flask, 23.68 g (70 mol %) of tetraethoxysilane, 1.61 g (5mol %) of phenyltrimethoxysilane, 2.31 g (8 mol %) oftriethoxymethylsilane, 2.58 g (5 mol %) oftrifluoroacetamidopropyltriethoxysilane, 0.79 g (2 mol %) of4-methoxybenzyltrimethoxysilane, 2.81 g (5 mol %) ofphenylsulfonylpropyltriethoxysilane, 2.67 g (5 mol %) of5-(triethoxysilyl)hexahydro-4,7-methanoisobenzofuran-1,3-dione, and53.50 g of acetone were poured and 10.83 g of 0.01 mol/l hydrochloricacid was added dropwise to the mixed solution with stirring the mixedsolution using a magnetic stirrer. After the addition, the flask wastransferred to an oil bath controlled to 85° C. and the solution wasreacted under heating reflux for 240 minutes. Thereafter, the reactionsolution was cooled to room temperature. To the reaction solution, 70.00g of propylene glycol monomethyl ether acetate was added. Methanol,ethanol, acetone, water, and hydrochloric acid as reaction byproductswere distilled off under reduced pressure and the reaction solution wasconcentrated to give the propylene glycol monomethyl ether acetatesolution of a hydrolysis condensate (polymer). To the solution,propylene glycol monoethyl ether was added so that the solution had aconcentration of 20% by mass in terms of solid residue at 140° C. in asolvent ratio of propylene glycol monomethyl ether acetate/propyleneglycol monoethyl ether of 20/80. The obtained polymer corresponded toFormula (2-4) and the weight average molecular weight Mw of the polymermeasured with GPC in terms of polystyrene was 1,700.

Synthesis Example 5

Into a 300 ml flask, 23.36 g (70 mol %) of tetraethoxysilane, 1.59 g (5mol %) of phenyltrimethoxysilane, 2.82 g (8 mol %) ofacetoxymethyltriethoxysilane, 2.54 g (5 mol %) oftrifluoroacetamidopropyltriethoxysilane, 0.78 g (2 mol %) of4-methoxybenzyltrimethoxysilane, 2.78 g (5 mol %) ofphenylsulfonylpropyltriethoxysilane, 2.63 g (5 mol %) of5-(triethoxysilyl)hexahydro-4,7-methanoisobenzofuran-1,3-dione, and53.59 g of acetone were poured and 10.68 g of 0.01 mol/l hydrochloricacid was added dropwise to the mixed solution with stirring the mixedsolution using a magnetic stirrer. After the addition, the flask wastransferred to an oil bath controlled to 85° C. and the solution wasreacted under heating reflux for 240 minutes. Thereafter, the reactionsolution was cooled to room temperature. To the reaction solution, 70.00g of propylene glycol monomethyl ether acetate was added. Methanol,ethanol, acetone, water, and hydrochloric acid as reaction byproductswere distilled off under reduced pressure and the reaction solution wasconcentrated to give the propylene glycol monomethyl ether acetatesolution of a hydrolysis condensate (polymer). To the solution,propylene glycol monoethyl ether was added so that the solution had aconcentration of 20% by mass in terms of solid residue at 140° C. in asolvent ratio of propylene glycol monomethyl ether acetate/propyleneglycol monoethyl ether of 20/80. The obtained polymer corresponded toFormula (2-5) and the weight average molecular weight Mw of the polymermeasured with GPC in terms of polystyrene was 2,100.

Synthesis Example 6

Into a 300 ml flask, 23.84 g (70 mol %) of tetraethoxysilane, 3.38 g (5mol %) of triethoxysilylpropyldiallyl isocyanurate, 5.83 g (20 mol %) ofmethyltriethoxysilane, 2.59 g (5 mol %) oftrifluoroacetamidopropyltriethoxysilane, and 53.46 g of acetone werepoured and 10.90 g of 0.01 mol/1 hydrochloric acid was added dropwise tothe mixed solution with stirring the mixed solution using a magneticstirrer. After the addition, the flask was transferred to an oil bathcontrolled to 85° C. and the solution was reacted under heating refluxfor 240 minutes. Thereafter, the reaction solution was cooled to roomtemperature. To the reaction solution, 70.00 g of propylene glycolmonomethyl ether acetate was added. Methanol, ethanol, acetone, water,and hydrochloric acid as reaction byproducts were distilled off underreduced pressure and the reaction solution was concentrated to give thepropylene glycol monomethyl ether acetate solution of a hydrolysiscondensate (polymer). To the solution, propylene glycol monoethyl etherwas added so that the solution had a concentration of 20% by mass interms of solid residue at 140° C. in a solvent ratio of propylene glycolmonomethyl ether acetate/propylene glycol monoethyl ether of 20/80. Theobtained polymer corresponded to Formula (2-6) and the weight averagemolecular weight Mw of the polymer measured with GPC in terms ofpolystyrene was 1,800.

Synthesis Example 7

Into a 300 ml flask, 24.74 g (70 mol %) of tetraethoxysilane, 1.68 g (5mol %) of phenyltrimethoxysilane, 5.75 g (19.9 mol %) ofmethyltriethoxysilane, 2.69 g (5 mol %) oftrifluoroacetamidopropyltriethoxysilane, 0.61 g (0.1 mol %) ofbenzenesulfonamidopropyltriethoxysilane, and 53.21 g of acetone werepoured and 11.31 g of 0.01 mol/1 hydrochloric acid was added dropwise tothe mixed solution with stirring the mixed solution using a magneticstirrer. After the addition, the flask was transferred to an oil bathcontrolled to 85° C. and the solution was reacted under heating refluxfor 240 minutes. Thereafter, the reaction solution was cooled to roomtemperature. To the reaction solution, 70.00 g of propylene glycolmonomethyl ether acetate was added. Methanol, ethanol, acetone, water,and hydrochloric acid as reaction byproducts were distilled off underreduced pressure and the reaction solution was concentrated to give thepropylene glycol monomethyl ether acetate solution of a hydrolysiscondensate (polymer). To the solution, propylene glycol monoethyl etherwas added so that the solution had a concentration of 20% by mass interms of solid residue at 140° C. in a solvent ratio of propylene glycolmonomethyl ether acetate/propylene glycol monoethyl ether of 20/80. Theobtained polymer corresponded to Formula (2-7) and the weight averagemolecular weight Mw of the polymer measured with GPC in terms ofpolystyrene was 1,800.

Synthesis Example 8

Into a 300 ml flask, 25.04 g (70 mol %) of tetraethoxysilane, 7.65 g (25mol %) of methyltriethoxysilane, 2.72 g (5 mol %) oftrifluoroacetamidopropyltriethoxysilane, and 53.13 g of acetone werepoured and 11.45 g of 1 mol/1 hydrochloric acid was added dropwise tothe mixed solution with stirring the mixed solution using a magneticstirrer. After the addition, the flask was transferred to an oil bathcontrolled to 85° C. and the solution was reacted under heating refluxfor 240 minutes. Thereafter, the reaction solution was cooled to roomtemperature. To the reaction solution, 70.00 g of propylene glycolmonomethyl ether acetate was added. Methanol, ethanol, acetone, water,and hydrochloric acid as reaction byproducts were distilled off underreduced pressure and the reaction solution was concentrated to give thepropylene glycol monomethyl ether acetate solution of a hydrolysiscondensate (polymer). To the solution, propylene glycol monoethyl etherwas added so that the solution had a concentration of 20% by mass interms of solid residue at 140° C. in a solvent ratio of propylene glycolmonomethyl ether acetate/propylene glycol monoethyl ether of 20/80. Theobtained polymer corresponded to Formula (2-8) and the weight averagemolecular weight Mw of the polymer measured with GPC in terms ofpolystyrene was 1,800.

Synthesis Example 9

Into a 300 ml flask, 21.79 g (70 mol %) of tetraethoxysilane, 14.23 g(30 mol %) of trifluoroacetamidopropyltriethoxysilane, and 54.02 g ofacetone were poured and 9.96 g of 1 mol/l hydrochloric acid was addeddropwise to the mixed solution with stirring the mixed solution using amagnetic stirrer. After the addition, the flask was transferred to anoil bath controlled to 85° C. and the solution was reacted under heatingreflux for 240 minutes. Thereafter, the reaction solution was cooled toroom temperature. To the reaction solution, 70.00 g of propylene glycolmonomethyl ether acetate was added. Methanol, ethanol, acetone, water,and hydrochloric acid as reaction byproducts were distilled off underreduced pressure and the reaction solution was concentrated to give thepropylene glycol monomethyl ether acetate solution of a hydrolysiscondensate (polymer). To the solution, propylene glycol monoethyl etherwas added so that the solution had a concentration of 20% by mass interms of solid residue at 140° C. in a solvent ratio of propylene glycolmonomethyl ether acetate/propylene glycol monoethyl ether of 20/80. Theobtained polymer corresponded to Formula (2-9) and the weight averagemolecular weight Mw of the polymer measured with GPC in terms ofpolystyrene was 1,800.

Comparative Synthesis Example 1

Into a 300 ml flask, 25.81 g (70 mol %) of tetraethoxysilane, 9.47 g (30mol %) of methyltriethoxysilane, and 52.92 g of acetone were poured and11.80 g of 0.01 mol/1 hydrochloric acid was added dropwise to the mixedsolution with stirring the mixed solution using a magnetic stirrer.After the addition, the flask was transferred to an oil bath controlledto 85° C. and the solution was reacted under heating reflux for 240minutes. Thereafter, the reaction solution was cooled to roomtemperature. To the reaction solution, 70.00 g of propylene glycolmonomethyl ether acetate was added. Methanol, ethanol, acetone, water,and hydrochloric acid as reaction byproducts were distilled off underreduced pressure and the reaction solution was concentrated to give thepropylene glycol monomethyl ether acetate solution of a hydrolysiscondensate (polymer). To the solution, propylene glycol monoethyl etherwas added so that the solution had a concentration of 20% by mass interms of solid residue at 140° C. in a solvent ratio of propylene glycolmonomethyl ether acetate/propylene glycol monoethyl ether of 20/80. Theobtained polymer corresponded to Formula (3-1) and the weight averagemolecular weight Mw of the polymer measured with GPC in terms ofpolystyrene was 1,700.

Comparative Synthesis Example 2

Into a 300 ml flask, 25.22 g (70 mol %) of tetraethoxysilane, 7.71 g (25mol %) of methyltriethoxysilane, 2.28 g (5 mol %) ofacetamidopropyltriethoxysilane, and 52.81 g of acetone were poured and11.53 g of 0.01 mol/1 hydrochloric acid was added dropwise to the mixedsolution with stirring the mixed solution using a magnetic stirrer.After the addition, the flask was transferred to an oil bath controlledto 85° C. and the solution was reacted under heating reflux for 240minutes. Thereafter, the reaction solution was cooled to roomtemperature. To the reaction solution, 70.00 g of propylene glycolmonomethyl ether acetate was added. Methanol, ethanol, acetone, water,and hydrochloric acid as reaction byproducts were distilled off underreduced pressure and the reaction solution was concentrated to give thepropylene glycol monomethyl ether acetate solution of a hydrolysiscondensate (polymer). To the solution, propylene glycol monoethyl etherwas added so that the solution had a concentration of 20% by mass interms of solid residue at 140° C. in a solvent ratio of propylene glycolmonomethyl ether acetate/propylene glycol monoethyl ether of 20/80. Theobtained polymer corresponded to Formula (3-2) and the weight averagemolecular weight Mw of the polymer measured with GPC in terms ofpolystyrene was 1,800.

(Preparation of Si—Containing Resist Underlayer Film)

The silicon-containing polymers obtained in Synthesis Examples 1 to 9and Comparative Synthesis Example 1 and Comparative Synthesis Example 2,an acid, a curing catalyst, an additive, solvents, and water were mixedin the ratios listed in Table 1, and the mixture was filtered with afluorocarbon resin filter of 0.1 μm to prepare each of the solutions ofthe resist underlayer film forming compositions. The addition ratio ofthe polymer in Table 1 is not the addition amount of the polymersolution but the addition amount of the polymer itself.

In Table 1, maleic acid is abbreviated as MA, benzyltriethylammoniumchloride as BTEAC, N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole asIMIDTEOS, triphenylsulfonium nitrate as TPSNO3, mono-triphenylsulfoniummaleate as TPSMA, triphenylsulfonium trifluoroacetate as TPSTFA,triphenylsulfonium chloride as TPSC1, triphenylsulfoniumcamphorsulfonate as TPSCS, triphenylsulfonium trifluoromethanesulfonateas TPSTf, triphenylsulfoniumadamantanecarboxy-1,1,2-trifluorobutanesulfonate as TPSAdTF,dihydroxyphenylphenylsulfonium p-toluenesulfonate as DHPPSpTS,bisphenylsulfone as BPS, propylene glycol monomethyl ether acetate asPGMEA, propylene glycol monoethyl ether as PGEE, and propylene glycolmonomethyl ether as PGME. As the water, ultrapure water was used. Eachamount to be added was listed in part by mass.

TABLE 1 Si Polymer Acid Curing catalyst Additive Solvent Example 1Synthesis Example 1 MA TPSNO3 TPSCS PGME PGEE PGMEA Water (part by mass)2 0.02 0.06  0.1 15 65 5 15 Example 2 Synthesis Example 2 MA TPSMA TPSTfPGME PGEE PGMEA Water (part by mass) 2 0.02 0.06   0.06 15 65 5 15Example 3 Synthesis Example 3 MA BTEAC TPSNf PGME PGEE PGMEA Water (partby mass) 2 0.02 0.012  0.06 15 65 5 15 Example 4 Synthesis Example 4 MAIMIDTEOS PGME PGEE PGMEA Water (part by mass) 2 0.02 0.006 15 65 5 15Example 5 Synthesis Example 5 MA IMIDTEOS DHTPPSpTS PGME PGEE PGMEAWater (part by mass) 2 0.02 0.006  0.06 15 65 5 15 Example 6 SynthesisExample 6 MA TPSTFA TPSAdTF PGME PGEE PGMEA Water (part by mass) 2 0.020.06  0.1 15 65 5 15 Example 7 Synthesis Example 7 MA TPSC1 BPS PGMEPGEE PGMEA Water (part by mass) 2 0.02 0.006 0.1 15 65 5 15 Example 8Synthesis Example 8 MA TPSNO3 TPSAdTF PGME PGEE PGMEA Water (part bymass) 2 0.02 0.006 0.1 15 65 5 15 Example 9 Synthesis Example 9 MATPSNO3 TPSAdTF PGME PGEE PGMEA Water (part by mass) 2 0.02 0.06  0.1 1565 5 15 Comparative Comparative MA TPSMA TPSTf PGME PGEE PGMEA WaterExample 1 Synthesis Example 1 0.02 0.006 0.1 15 65 5 15 (part by mass) 2Comparative Comparative MA TPSNO3 PGME PGEE PGMEA Water Example 2Synthesis Example 2 0.02 0.06  15 65 5 15 (part by mass) 2

(Preparation of Organic Underlayer Film-Forming Composition)

Into a 100 mL four-necked flask, carbonazole (6.69 g, 0.040 mol,manufactured by Tokyo Chemical Industry Co., Ltd.), 9-fluorenone (7.28g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.),p-toluenesulfonic acid monohydrate (0.76 g, 0.0040 mol, manufactured byTokyo Chemical Industry Co., Ltd.) were placed and then 1,4-dioxane(6.69 g, manufactured by KANTO CHEMICAL CO., INC.) was charged undernitrogen. The mixture was stirred and heated to 100° C. to dissolve themixture and polymerization was started. After 24 hours, the solution wasleft to cool to 60° C., diluted with chloroform (34 g, manufactured byKANTO CHEMICAL CO., INC.), and reprecipitated in methanol (168 g,manufactured by KANTO CHEMICAL CO., INC.). The obtained precipitate wasfiltered and dried at 80° C. for 24 hours in a reduced pressure drier togive 9.37 g of a target polymer (Formula (4-1), hereinafter abbreviatedas PCzFL).

The measurement result of ¹H-NMR of PCzFL was as follows.

¹H-NMR (400 MHz, DMSO-d₆): δ 7.03-7.55 (br, 12H), δ 7.61-8.10 (br, 4H),δ 11.18 (br, 1H)

The weight average molecular weight Mw and the degree of distributionMw/Mn of PCzFL measured by GPC in terms of polystyrene were 2,800 and1.77, respectively.

To 20 g of the obtained resin, 3.0 g of tetramethoxymethylglycoluril(trade name POWDERLINK 1174, manufactured by Mitsui Cytec, Ltd.) as acrosslinking agent, 0.30 g of pyridinium paratoluenesulfonate as acatalyst, and 0.06 g of Megafac R-30N (trade name, manufactured by DICCorporation) were mixed and the mixture was dissolved in 88 g ofpropylene glycol monomethyl ether acetate to prepare a solution.Thereafter, the mixture was filtered using a polyethylene microfilterhaving a pore diameter of 0.10 μm and further filtered using apolyethylene microfilter having a pore size of 0.05 μm to prepare asolution of the organic underlayer film forming composition used for alithography process using a multilayer film.

(Optical Constant Measurement)

Each of the Si-containing resist underlayer film forming compositionsprepared in Examples 1 to 9 and Comparative Examples 1 and 2 was appliedonto a silicon wafer using a spinner. The applied composition was heatedon a hot plate at 200° C. for 1 minute to form a Si-containing resistunderlayer film (film thickness: 0.05 μm). The refractive indices (nvalues) and optical absorption coefficients (also referred to as kvalues or attenuation coefficients) of these resist underlayer films ata wavelength of 193 nm were measured using a spectroscopic ellipsometer(VUV-VASEVU-302, manufactured by J. A. Woollam Co., Inc.).

(Measurement of Dry Etching Rate)

The etchers and etching gases used for the measurement of the dryetching rate were as follows.

ES 401 (manufactured by Nippon Scientific Co., Ltd.): CF₄

RIE-10NR (manufactured by Samco Inc.): O₂

Each of the solutions of the Si-containing resist underlayer filmforming compositions prepared in Examples 1 to 9 and ComparativeExamples 1 and 2 was applied onto a silicon wafer using a spinner. Eachof the Si-containing resist underlayer films (film thickness 0.08 μm(for measurement of the etching rate with CF₄ gas)) and (film thickness0.05 μm (for measurement of the etching rate with O₂ gas)) was formed byheating the applied solution on a hot plate at 240° C. for 1 minute.Similarly, the coating film of the organic underlayer film formingcomposition (composition containing the polymer of Formula (4-1)) (filmthickness: 0.20 μm) was also formed on a silicon wafer using a spinner.

The dry etching rates of the Si-containing resist underlayer films ofExamples 1 to 9 and Comparative Examples 1 and 2 were measured using CF₄gas as an etching gas and compared with each other. The unit of the testresult of the fluorine-based gas etching rate is angstrom/min.

The dry etching rates of the Si-containing resist underlayer films ofExamples 1 to 9 and Comparative Examples 1 and 2 were measured using O₂gas as an etching gas and compared with each other. The unit of the testresult of the oxygen-based gas resistance is angstrom/min.

(Evaluation of Resist Patterning: Evaluation Through NTD ProcessPerforming Development with Organic Solvent)

The organic underlayer film (A layer) forming composition obtained asthe above formula was applied onto a silicon wafer and baked on a hotplate at 240° C. for 60 seconds to give an organic underlayer film(layer A) having a thickness of 200 nm. Onto the organic underlayerfilm, each of the Si-containing resist underlayer film (layer B) formingcompositions obtained in Examples 1 to 9 and Comparative Examples 1 and2 was applied and baked on a hot plate at 240° C. for 60 seconds to givea Si-containing resist underlayer film (layer B). The film thickness ofthe Si-containing resist underlayer film (layer B) was 30 nm.

Onto each of the B layers, a commercially available photoresist solution(manufactured by Fujifilm Corporation, trade name FAiRS-9521NT05) wasapplied by a spinner and heated on a hot plate at 100° C. for 1 minuteto form a photoresist film (C layer) having a thickness of 85 nm.

The obtained photoresist film was exposed using an NSR-S307E scanner(wavelength 193 nm, NA, a: 0.85, 0.93/0.85, manufactured by NikonCorporation) through a mask that is set so that a line width and a widthbetween the lines of the photoresist of 0.060 μm, that is, dense lineshaving a line and space (L/S)=1/2 of 0.060 μm were formed after thedevelopment and a mask that is set so that a line width and a widthbetween the lines of the photoresist of 0.058 μm, that is, dense lineshaving a line and space (L/S)=1/1 of 0.058 μm were formed after thedevelopment. Thereafter, the exposed resist was baked on a hot plate at100° C. for 60 seconds, cooled, and thereafter developed for 60 secondsusing butyl acetate (a solvent developer) to form a negative pattern onthe resist underlayer film (layer B). With regard to the obtainedphotoresist pattern, a pattern that did not cause large pattern peeling,undercut, and thickening at the bottom of the line (footing) wasevaluated as good.

In Table 2, the results of the refractive index and optical absorptioncoefficient at 193 nm, the fluorine gas etching rate, the oxygen-basedgas resistance, and the skirt shape of the resist after lithographyevaluation are listed.

TABLE 2 Fluorine- Refrac- Optical based gas Oxygen- tive absorptionetching based gas Resist skirt index coefficient rate resistance shapeExample 1 1.65 0.14 24 0.02 Good Example 2 1.60 0.25 25 0.03 GoodExample 3 1.70 0.35 26 0.04 Good Example 4 1.68 0.33 27 0.04 GoodExample 5 1.68 0.33 27 0.04 Good Example 6 1.64 0.14 30 0.03 GoodExample 7 1.64 0.18 24 0.02 Good Example 8 1.56 0.08 23 0.02 GoodExample 9 1.56 0.08 28 0.04 Good Comparative 1.55 0.01 22 0.03 UndercutExample 1 Comparative 1.57 0.07 23 0.03 Footing Example 2

[Formation of Resist Pattern by EUV Exposure]

The organic underlayer film (A layer) forming composition was appliedonto a silicon wafer and baked on a hot plate at 215° C. for 60 secondsto give an organic underlayer film (layer A) having a thickness of 90nm. On the A layer, the resist underlayer film forming compositionsolutions prepared in Examples 1, 6, 7, 8 and 9 of the present inventionand Comparative Examples 1 and 2 were spin-coated and heated at 215° C.for 1 minute to form a resist underlayer film (layer B) (20 nm). On thehard mask, an EUV resist solution (methacrylate resin type resist) wasspin-coated and heated to form an EUV resist layer (C layer). The EUVresist layer was exposed using an EUV exposure apparatus (Micro ExposureTool, abbreviated as MET) under conditions of NA=0.30, σ=0.36/0.93, andQuadropole. After the exposure, PEB (post exposure bake) was carried outand the exposed sample was cooled to room temperature on a coolingplate, followed by developing and rinsing the sample to form a resistpattern. For the obtained resist pattern, a possibility of formation of26 nm line and space and the pattern shape by observing the patterncross section were evaluated.

In Table 3, “Good” means a state in which a shape between the footingand the undercut is rectangular and no significant residue in the spaceportion remains, “Collapsed” means an undesirable state in which theresist pattern is peeled and collapsed, and “Bridged” means anundesirable state in which the upper part or the lower part of theresist pattern is in contact with each other.

TABLE 3 Pattern shape Example 1 Good Example 6 Good Example 7 GoodExample 8 Good Example 9 Good Comparative Collapsed Example 1Comparative Bridged Example 2

INDUSTRIAL APPLICABILITY

The resist underlayer film forming composition for lithography of thepresent invention can be used for a resist underlayer film formingcomposition for an ArF photoresist and a KrF photoresist, a resistunderlayer film forming composition for an EUV resist or the like, aresist upper layer forming composition for an EUV resist, a resistunderlayer film forming composition for an electron beam resist or thelike, a resist upper layer forming composition for an electron beamresist, a reverse material forming composition, and the like.

1. A resist underlayer film forming composition for lithographycomprising: a hydrolyzable silane, a hydrolysis product thereof, ahydrolysis condensate thereof, or a combination thereof as a silane,wherein the hydrolyzable silane comprises a hydrolyzable silane having ahalogen-containing carboxylic acid amide group.
 2. The resist underlayerfilm forming composition according to claim 1, wherein the hydrolyzablesilane having a halogen-containing carboxylic acid amide group is ahydrolyzable silane of Formula (1):R¹ _(a)R² _(b)Si(R³)_(4-(a+b))  Formula (1) (in Formula (1), R¹ is anorganic group of Formula (2):

(in Formula (2), R⁴ is an organic group optionally having an amidegroup, an amino group, an ether group, or a sulfonyl group and theorganic group is a C₁₋₁₀ alkylene group, an arylene group, or acombination thereof; R⁵ is a hydrogen atom or a C₁₋₁₀ alkyl group; R⁶ isan organic group substituted with a halogen atom or an organic grouphaving a halogen ion and the organic group is a C₁₋₁₀ alkyl group, aC₃₋₂₀ cyclic alkyl group, a C₁₋₁₀ alkylene group, a C₆₋₄₀ aryl group, aC₆₋₄₀ arylene group, a heterocyclic group, or a combination thereofoptionally having a sulfonyl group, a thiol group, an ether group, or acarbonyl group) and is bonded to a silicon atom through a Si—C bond; R²is an organic group having an alkyl group, an aryl group, a halogenatedalkyl group, a halogenated aryl group, an alkoxyaryl group, an alkenylgroup, or an epoxy group, an acryloyl group, a methacryloyl group, amercapto group, an amino group, or a cyano group and is bonded to asilicon atom through a Si—C bond; R³ is an alkoxy group, an acyloxygroup, or a halogen group; a is an integer of 1, b is an integer of 0 to2, and a+b is an integer of 1 to 3).
 3. The resist underlayer filmforming composition according to claim 1, wherein a halogen atom in thehalogen-containing carboxylic acid amide group is a fluorine atom. 4.The resist underlayer film forming composition according to claim 1,wherein the halogen-containing carboxylic acid amide group is atrifluoroacetamide group.
 5. The resist underlayer film formingcomposition according to claim 1, wherein the hydrolyzable silane is acombination of the hydrolyzable silane of Formula (1) and otherhydrolyzable silane, and the other hydrolyzable silane is at least onehydrolyzable silane selected from the group consisting of a hydrolyzablesilane of Formula (3):R⁷ _(c)Si(R⁸)_(4-c)  Formula (3) (in Formula (3), R⁷ is an organic grouphaving an alkyl group, an aryl group, a halogenated alkyl group, ahalogenated aryl group, an alkoxyaryl group, an alkenyl group, or anepoxy group, an acryloyl group, a methacryloyl group, a mercapto group,or a cyano group and is bonded to a silicon atom through a Si—C bond; R⁸is an alkoxy group, an acyloxy group, or a halogen group; and c is aninteger of 0 to 3) and a hydrolyzable silane of Formula (4):

R⁹ _(d)Si(R¹⁰)_(3-d)

₂Y_(e)  Formula (4) (in Formula (4), R⁹ is an alkyl group and is bondedto a silicon atom through a Si—C bond; R¹⁰ is an alkoxy group, anacyloxy group, or a halogen group; Y is an alkylene group or an arylenegroup; d is an integer of 0 or 1; and e is an integer of 0 or 1).
 6. Theresist underlayer film forming composition according to claim 1, whereinthe resist underlayer film forming composition comprises a hydrolysiscondensate of a hydrolyzable silane made of a combination of thehydrolyzable silane of Formula (1)R¹ _(a)R² _(b)Si(R³)_(4-(a+b))  Formula (1) (in Formula (1), R¹ is anorganic group of Formula (2)) and the hydrolyzable silane of Formula (3)R⁷ _(c)Si(R⁸)_(4-c)

  Formula (3) (in Formula (3), R⁷ is an organic group having an alkylgroup, an aryl group, a halogenated alkyl group, a halogenated arylgroup, an alkoxyaryl group, an alkenyl group, or an epoxy group, anacryloyl group, a methacryloyl group, a mercapto group, or a cyano groupand is bonded to a silicon atom through a Si—C bond: R⁸ is an alkoxygroup, an acyloxy group, or a halogen group; and c is an integer of 0 to3) as a polymer.
 7. The resist underlayer film forming compositionaccording to claim 1, further comprising an acid.
 8. The resistunderlayer film forming composition according to claim 1, furthercomprising water.
 9. A resist underlayer film formed on a semiconductorsubstrate and made of a cured product of the resist underlayer filmforming composition as claimed in claim
 1. 10. A method formanufacturing a semiconductor device, the method comprising: applyingthe resist underlayer film forming composition as claimed in claim 1onto a semiconductor substrate and baking the applied composition toform a resist underlayer film; applying a resist composition onto theresist underlayer film to form a resist film; exposing the resist filmto light; developing the resist film after exposure to obtain a resistpattern; etching the resist underlayer film using the resist pattern;and processing the semiconductor substrate using the patterned resistfilm and resist underlayer film.
 11. A method for manufacturing asemiconductor device, the method comprising: forming an organicunderlayer film on a semiconductor substrate; applying a resistunderlayer film forming composition according to claim 1 onto theorganic underlayer film and baking the applied composition to form aresist underlayer film; applying a resist composition onto the resistunderlayer film to form a resist film; exposing the resist film tolight; developing the resist film after exposure to obtain a resistpattern; etching the resist underlayer film using the resist pattern;etching the organic underlayer film using the patterned resistunderlayer film; and processing the semiconductor substrate using thepatterned organic underlayer film.